Oxygen-evolving complex

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The Kok cycle. Note that the oxidation state of the manganese centres is subject to debate. Kok-cycle.svg
The Kok cycle. Note that the oxidation state of the manganese centres is subject to debate.
X-ray crystal structure of the Mn4O5Ca core of the oxygen evolving complex of Photosystem II at a resolution of 1.9 A. Oxygen Evolving Complex Crystal structure to 1.9 Angstrom Resolution.png
X-ray crystal structure of the Mn4O5Ca core of the oxygen evolving complex of Photosystem II at a resolution of 1.9 Å.

The oxygen-evolving complex (OEC), also known as the water-splitting complex, is a water-oxidizing enzyme involved in the photo-oxidation of water during the light reactions of photosynthesis. [2] OEC is surrounded by 4 core proteins of photosystem II at the membrane-lumen interface. The mechanism for splitting water involves absorption of three photons before the fourth provides sufficient energy for water oxidation. [3] Based on a widely accepted theory from 1970 by Kok, the complex can exist in 5 states, denoted S0 to S4, with S0 the most reduced and S4 the most oxidized. Photons trapped by photosystem II move the system from state S0 to S4. S4 is unstable and reacts with water producing free oxygen. For the complex to reset to the lowest state, S0, it uses 2 water molecules to pull out 4 electrons.

The OEC active site contains a cluster of manganese and calcium, with the formula Mn4Ca1OxCl1–2(HCO3)y. This cluster is coordinated by D1 and CP43 subunits and stabilized by peripheral membrane proteins. Other characteristics of it have been reviewed. [4]

Currently, the mechanism of the complex is not completely understood. [5] [6] Along with the role of Ca+2, Cl−1, and the membrane proteins surrounding the metal cluster not being well understood. Much of what is known has been collected from flash photolysis experiments, electron paramagnetic resonance (EPR), and X-ray spectroscopy. [7]

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<span class="mw-page-title-main">Photosynthesis</span> Biological process to convert light into chemical energy

Photosynthesis is a biological process used by many cellular organisms to convert light energy into chemical energy, which is stored in organic compounds that can later be metabolized through cellular respiration to fuel the organism's activities. The term usually refers to oxygenic photosynthesis, where oxygen is produced as a byproduct, and some of the chemical energy produced is stored in carbohydrate molecules such as sugars, starch, glycogen and cellulose, which are synthesized from endergonic reaction of carbon dioxide with water. Most plants, algae and cyanobacteria perform photosynthesis; such organisms are called photoautotrophs. Photosynthesis is largely responsible for producing and maintaining the oxygen content of the Earth's atmosphere, and supplies most of the biological energy necessary for complex life on Earth.

<span class="mw-page-title-main">Thylakoid</span> Membrane enclosed compartments in chloroplasts and cyanobacteria

Thylakoids are membrane-bound compartments inside chloroplasts and cyanobacteria. They are the site of the light-dependent reactions of photosynthesis. Thylakoids consist of a thylakoid membrane surrounding a thylakoid lumen. Chloroplast thylakoids frequently form stacks of disks referred to as grana. Grana are connected by intergranal or stromal thylakoids, which join granum stacks together as a single functional compartment.

<span class="mw-page-title-main">Photosystem</span> Structural units of protein involved in photosynthesis

Photosystems are functional and structural units of protein complexes involved in photosynthesis. Together they carry out the primary photochemistry of photosynthesis: the absorption of light and the transfer of energy and electrons. Photosystems are found in the thylakoid membranes of plants, algae, and cyanobacteria. These membranes are located inside the chloroplasts of plants and algae, and in the cytoplasmic membrane of photosynthetic bacteria. There are two kinds of photosystems: PSI and PSII.

<span class="mw-page-title-main">Photosystem II</span> First protein complex in light-dependent reactions of oxygenic photosynthesis

Photosystem II is the first protein complex in the light-dependent reactions of oxygenic photosynthesis. It is located in the thylakoid membrane of plants, algae, and cyanobacteria. Within the photosystem, enzymes capture photons of light to energize electrons that are then transferred through a variety of coenzymes and cofactors to reduce plastoquinone to plastoquinol. The energized electrons are replaced by oxidizing water to form hydrogen ions and molecular oxygen.

<span class="mw-page-title-main">Photosystem I</span> Second protein complex in photosynthetic light reactions

Photosystem I is one of two photosystems in the photosynthetic light reactions of algae, plants, and cyanobacteria. Photosystem I is an integral membrane protein complex that uses light energy to catalyze the transfer of electrons across the thylakoid membrane from plastocyanin to ferredoxin. Ultimately, the electrons that are transferred by Photosystem I are used to produce the moderate-energy hydrogen carrier NADPH. The photon energy absorbed by Photosystem I also produces a proton-motive force that is used to generate ATP. PSI is composed of more than 110 cofactors, significantly more than Photosystem II.

Artificial photosynthesis is a chemical process that biomimics the natural process of photosynthesis to convert sunlight, water, and carbon dioxide into carbohydrates and oxygen. The term artificial photosynthesis is commonly used to refer to any scheme for capturing and storing the energy from sunlight in the chemical bonds of a fuel. Photocatalytic water splitting converts water into hydrogen and oxygen and is a major research topic of artificial photosynthesis. Light-driven carbon dioxide reduction is another process studied that replicates natural carbon fixation.

<span class="mw-page-title-main">Water splitting</span> Chemical reaction

Water splitting is the chemical reaction in which water is broken down into oxygen and hydrogen:

Photodissociation, photolysis, photodecomposition, or photofragmentation is a chemical reaction in which molecules of a chemical compound are broken down by photons. It is defined as the interaction of one or more photons with one target molecule.

<span class="mw-page-title-main">Photosynthetic reaction centre</span> Molecular unit responsible for absorbing light in photosynthesis

A photosynthetic reaction center is a complex of several proteins, pigments and other co-factors that together execute the primary energy conversion reactions of photosynthesis. Molecular excitations, either originating directly from sunlight or transferred as excitation energy via light-harvesting antenna systems, give rise to electron transfer reactions along the path of a series of protein-bound co-factors. These co-factors are light-absorbing molecules (also named chromophores or pigments) such as chlorophyll and pheophytin, as well as quinones. The energy of the photon is used to excite an electron of a pigment. The free energy created is then used, via a chain of nearby electron acceptors, for a transfer of hydrogen atoms (as protons and electrons) from H2O or hydrogen sulfide towards carbon dioxide, eventually producing glucose. These electron transfer steps ultimately result in the conversion of the energy of photons to chemical energy.

<span class="mw-page-title-main">Photoinhibition</span>

Photoinhibition is light-induced reduction in the photosynthetic capacity of a plant, alga, or cyanobacterium. Photosystem II (PSII) is more sensitive to light than the rest of the photosynthetic machinery, and most researchers define the term as light-induced damage to PSII. In living organisms, photoinhibited PSII centres are continuously repaired via degradation and synthesis of the D1 protein of the photosynthetic reaction center of PSII. Photoinhibition is also used in a wider sense, as dynamic photoinhibition, to describe all reactions that decrease the efficiency of photosynthesis when plants are exposed to light.

Oxygenevolution is the process of generating molecular oxygen (O2) by a chemical reaction, usually from water. Oxygen evolution from water is effected by oxygenic photosynthesis, electrolysis of water, and thermal decomposition of various oxides. The biological process supports aerobic life. When relatively pure oxygen is required industrially, it is isolated by distilling liquefied air.

<span class="mw-page-title-main">Photosynthetic reaction centre protein family</span>

Photosynthetic reaction centre proteins are main protein components of photosynthetic reaction centres (RCs) of bacteria and plants. They are transmembrane proteins embedded in the chloroplast thylakoid or bacterial cell membrane.

<span class="mw-page-title-main">Cytochrome b559</span> Family of protein complexes

Cytochrome b559 is an important component of Photosystem II (PSII) is a multisubunit protein-pigment complex containing polypeptides both intrinsic and extrinsic to the photosynthetic membrane. Within the core of the complex, the chlorophyll and beta-carotene pigments are mainly bound to the antenna proteins CP43 (PsbC) and CP47 (PsbB), which pass the excitation energy on to chlorophylls in the reaction centre proteins D1 and D2 that bind all the redox-active cofactors involved in the energy conversion process. The PSII oxygen-evolving complex (OEC) provides electrons to re-reduce the PSII reaction center, and oxidizes 2 water molecules to recover its reduced initial state. It consists of OEE1 (PsbO), OEE2 (PsbP) and OEE3 (PsbQ). The remaining subunits in PSII are of low molecular weight, and are involved in PSII assembly, stabilisation, dimerization, and photoprotection.

Dioxygen plays an important role in the energy metabolism of living organisms. Free oxygen is produced in the biosphere through photolysis of water during photosynthesis in cyanobacteria, green algae, and plants. During oxidative phosphorylation in cellular respiration, oxygen is reduced to water, thus closing the biological water-oxygen redox cycle.

<span class="mw-page-title-main">Manganese in biology</span> Use of manganese by organisms

Manganese is an essential biological element in all organisms. It is used in many enzymes and proteins. It is essential in plants.

<span class="mw-page-title-main">Light-dependent reactions</span> Photosynthetic reactions

Light-dependent reactions refers to certain photochemical reactions that are involved in photosynthesis, the main process by which plants acquire energy. There are two light dependent reactions, the first occurs at photosystem II (PSII) and the second occurs at photosystem I (PSI).

A transition metal oxo complex is a coordination complex containing an oxo ligand. Formally O2-, an oxo ligand can be bound to one or more metal centers, i.e. it can exist as a terminal or (most commonly) as bridging ligands (Fig. 1). Oxo ligands stabilize high oxidation states of a metal. They are also found in several metalloproteins, for example in molybdenum cofactors and in many iron-containing enzymes. One of the earliest synthetic compounds to incorporate an oxo ligand is potassium ferrate (K2FeO4), which was likely prepared by Georg E. Stahl in 1702.

Plastid terminal oxidase or plastoquinol terminal oxidase (PTOX) is an enzyme that resides on the thylakoid membranes of plant and algae chloroplasts and on the membranes of cyanobacteria. The enzyme was hypothesized to exist as a photosynthetic oxidase in 1982 and was verified by sequence similarity to the mitochondrial alternative oxidase (AOX). The two oxidases evolved from a common ancestral protein in prokaryotes, and they are so functionally and structurally similar that a thylakoid-localized AOX can restore the function of a PTOX knockout.

Evolution of metal ions in biological systems refers to the incorporation of metallic ions into living organisms and how it has changed over time. Metal ions have been associated with biological systems for billions of years, but only in the last century have scientists began to truly appreciate the scale of their influence. Major and minor metal ions have become aligned with living organisms through the interplay of biogeochemical weathering and metabolic pathways involving the products of that weathering. The associated complexes have evolved over time.

<span class="mw-page-title-main">Water oxidation catalysis</span>

Water oxidation catalysis (WOC) is the acceleration (catalysis) of the conversion of water into oxygen and protons:

References

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  2. Raymond, J.; Blankenship, R. (2008). "The origin of the oxygen-evolving complex". Coordination Chemistry Reviews. 252 (3–4): 377–383. doi:10.1016/j.ccr.2007.08.026.
  3. Johnson, James. "The Origin of Life - The Rise of the Oxygen Evolving Complex". www.chm.bris.ac.uk. Florida University. Retrieved 2020-04-30.
  4. Abstract : Manganese: The Oxygen-Evolving Complex & Models1 : Encyclopedia of Inorganic Chemistry : Wiley InterScience
  5. Askerka, Mikhail; Brudvig, Gary W.; Batista, Victor S. (2017). "The O2-Evolving Complex of Photosystem II: Recent Insights from Quantum Mechanics/Molecular Mechanics (QM/MM), Extended X-ray Absorption Fine Structure (EXAFS), and Femtosecond X-ray Crystallography Data". Accounts of Chemical Research. 50 (1): 41–48. doi: 10.1021/acs.accounts.6b00405 . PMID   28001034.
  6. Yano, Junko; Kern, Jan; Yachandra, Vittal K.; Nilsson, Håkan; Koroidov, Sergey; Messinger, Johannes (2015). "Light-Dependent Production of Dioxygen in Photosynthesis". In Peter M.H. Kroneck and Martha E. Sosa Torres (ed.). Sustaining Life on Planet Earth: Metalloenzymes Mastering Dioxygen and Other Chewy Gases. Metal Ions in Life Sciences. Vol. 15. Springer. pp. 13–43. doi:10.1007/978-3-319-12415-5_2. ISBN   978-3-319-12414-8. PMC   4688042 . PMID   25707465.
  7. Kok, B.; Forbush, B.; McGloin, M. (1970). "Cooperation of charges in photosynthetic O2 evolution. I. A linear four-step mechanism". Photochem. Photobiol. 11 (6): 467–475. doi:10.1111/j.1751-1097.1970.tb06017.x. PMID   5456273. S2CID   31914925.