Week 8 Johnson Lecture 4 Flashcards
What does PSII do?
A biological enzyme that is capable of oxidising H2O to O2 and It reduces PQ to PQH
the special pair chlorophylls P680 are the primary electron donor
What is the redox scheme for PSII?
To achieve the splitting of water a redox potential (the difference) of greater than +820 mV is required. The P680+/P680 redox couple has a redox potential of +1200 mV while Yz+/ Yz has a redox potential of +950 mv, thus they can act as oxidants H2O/O2 couple.The P680*/P680+ redox couple has a redox potential of -630 mV
How much energy does light contain?
Calculation;
ΔG=(Nhc)/λ
(gives us the energy of one mole of photons)
N = Avogadro’s number = 6.02 × 1023
h = Planck’s constant = 6.63 × 10-34 j × s
c = speed of light in a vacuum = 3 ×108 m s-1 λ = wavelength of the light
e.g. 1 mole of 680 nm (680 × 10-9 m) photons
E=((6.02 × 1023) × (6.63 × 10-34) × (3 × 108))/(680 × 10-9) ΔG = 176085 J mol-1
ΔG = 176 kJ mol-1
What are the energetics of the PSII reaction?
Overall reaction:
2H2O + 2PQ + 4H+stroma —–> O2 + 2PQH2 + 4H+lumen
oxidises H2O to O2 (E0’ =+820 mV) it reduces PQ to PQH2 (E0’ =+80 mV)
ΔE0’ = E0’(acceptor)- E0’(donor) ΔE0’ = +80 - (+820)
ΔE0’ = -740 mV
ΔG = -nFΔE0’ (n = moles of electrons transferred, F= Faraday constant) ΔG = -4 × 96.5 × 10-3 ×-740
ΔG = +285 kJ mol-1
This free energy input is provided by 4 x 680 nm photons
(176 kJ mol-1 each = 704 kJ mol-1) 285/704 = 40% efficiency
What do the cofactors that take part in the electron transfer reactions in PSII do? and what are they?
At the heart of the PSII reaction centre are several key co- factors which take part in electron transfer reactions from water to plastoquinone. they are ; -Fe2+ -Plastoquinone (Qa) -Plastoquinone (Qb) -Pheophytin (PheoA) -Pheophytin (Pheob) -Chlorophyll a a -Chlorophyll a b -Chlorophyll a P680A/P680B -Tyrosine161 (Yz) -Manganese cluster (Mn4CaO5)
How does PSII work?
Basically
- Chlorophyll a P680A/P680B is excited, charges separate to positive and negative
- The negative electron is donated from the special pair to accessory pigments; Chlorophyll a a to Pheophytin A to Plastoquinone A to Plastoquinone B
- Positive charge is still in special pair
- Manganese cluster attracts water molecule and an electron from water is taken and transferred to special pair, transfer occurs via tyrosine161
- P680 is now regenerated
- Proton from manganese cluster leaves stroma
- -It takes 2 turnovers (2 photons) to make 1 PGH2
- -it takes 4 turnovers (4 photons) to male 1 O2
What is plastoquinone?
Plastoquinone, a lipid soluble electron carrier shares a very similar structure to ubiquinone, which is present in mitochondria and bacteria. The 2 e- are used to reduce the two C=O carbon atoms from +2 to +1 oxidation state, forming two -OH groups.
What ensures that the charges are kept separate?
To ensure this, a chain of electron acceptors which are energetically ‘downhill’ from P680* ensures e- and hole (+) are rapidly separated spatially (electron transfer efficiency decays exponentially with distance), slowing down the reverse reactions and stabilising charge separation. This minimises energy loss as heat via recombination of ChlA- and P680+