Q.35 The water splitting in photo system-II (PSD) is mediated by metal Mn Mg Fe Ni

Q.35 The water splitting in photo system-II (PSD) is mediated by metal

  1. Mn
  2. Mg
  3. Fe
  4. Ni

    Mn (Manganese) is the metal mediating water splitting in Photosystem II (PSII) (Option A).

    In PSII’s oxygen-evolving complex (OEC), a Mn4CaO5 cluster catalyzes water oxidation (2H₂O → O₂ + 4H⁺ + 4e⁻) during the S-state cycle, driven by light-induced P680⁺ oxidation.

    Option Breakdown

    • Mn: Correct. Four Mn ions (Mn³⁺/Mn⁴⁺ states) form a cubane-like cluster with Ca²⁺, bridging oxo ligands to enable four-electron water splitting without harmful radicals.

    • Mg: Central to chlorophyll (Mg-porphyrin) for light harvesting in both photosystems; no role in PSII water oxidation.

    • Fe: Key in PSI (Fe-S clusters for electron transfer), cytochromes (e.g., cyt b6f), and ferredoxin; absent from OEC.

    • Ni: Found in urease/hydrogenases, not photosynthetic complexes; irrelevant to PSII photochemistry.

    Water splitting in photosystem II (PSII) is mediated by Mn in the oxygen-evolving complex (OEC), producing all atmospheric O₂ via the S0-S4 cycle. This Mn4Ca cluster accumulates four oxidizing equivalents from P680 to oxidize two H₂O molecules.

    OEC Mechanism Overview

    Light excites P680 → P680⁺, oxidizing Yz (tyrosine) which extracts electrons from Mn cluster over four flashes (Kok cycle). Mn oxidation states shift (e.g., Mn³⁺ → Mn⁴⁺), culminating in O-O bond formation and O₂ release.

    Metal Role Comparison

    Metal Role in PSII Water Splitting? Primary Function
    Mn Yes (OEC cluster) Catalyzes 2H₂O → O₂ 
    Mg No Chlorophyll core 
    Fe No PSI electron carriers 
    Ni No Non-photosynthetic enzymes

    Critical for exam prep on light reactions and bioinorganic catalysis.

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