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The process of oxidizing two molecules of water to form an oxygen molecule requires four electrons. The water molecules that are oxidized in the manganese center are the source of the electrons that reduce the two molecules of Q to QH 2. To date, this water splitting catalytic center has not been reproduced by any man-made catalyst.
Water oxidation is catalyzed by a manganese-containing cofactor contained in photosystem II, known as the oxygen-evolving complex (OEC) or the water-splitting complex. Manganese is an important cofactor, and calcium and chloride are also required for the reaction to occur. [4] The stoichiometry of this reaction is as follows: 2H 2 O 4e − + 4H ...
It is a metallo-oxo cluster comprising four manganese ions (in oxidation states ranging from +3 to +4) [6] and one divalent calcium ion. When it oxidizes water, producing oxygen gas and protons, it sequentially delivers the four electrons from water to a tyrosine (D1-Y161) sidechain and then to P680 itself.
S 4 reacts with water producing free oxygen: 2 H 2 O → O 2 + 4 H + + 4 e −. This conversion resets the catalyst to the S 0 state. The active site of the OEC consists of a cluster of manganese and calcium with the formula Mn 4 Ca 1 O x Cl 1–2 (HCO 3) y. This cluster is bound to D 1 and CP 43 subunits and stabilized by peripheral membrane ...
Manganese dioxide, which is abundant in nature, has long been used as a pigment. The cave paintings in Gargas that are 30,000 to 24,000 years old are made from the mineral form of MnO 2 pigments. [43] Manganese compounds were used by Egyptian and Roman glassmakers, either to add to, or remove, color from glass. [44]
In a classical laboratory demonstration, heating a mixture of potassium chlorate and manganese dioxide produces oxygen gas. Manganese dioxide also catalyses the decomposition of hydrogen peroxide to oxygen and water: 2 H 2 O 2 → 2 H 2 O + O 2. Manganese dioxide decomposes above about 530 °C to manganese(III) oxide and oxygen.
Manganese is also important in photosynthetic oxygen evolution in chloroplasts in plants. The oxygen-evolving complex (OEC) is a part of photosystem II contained in the thylakoid membranes of chloroplasts; it is responsible for the terminal photooxidation of water during the light reactions of photosynthesis , and has a metalloenzyme core ...
Water oxidation is a more complex chemical reaction than proton reduction. In nature, the oxygen-evolving complex performs this reaction by accumulating reducing equivalents (electrons) in a manganese-calcium cluster within photosystem II (PS II), then delivering them to water molecules, with the resulting production of molecular oxygen and ...