Energy in biosphere Flashcards
High energy chemicals for life produced by resp
ATP, NADH, NADPH
How long ago did multicellular life form
1.5 giga years before now
What does oxygenic photosynthesis involve
Water splitting
How did photosynthesisers colonise the planet
By using water as a source of electrons
How did O2 change the planet
- World became aerobic 2. O2 converted to O3 (ozone) by UV in stratosphere - ozone screens out UV allowing life to come out from under the stones 3. Respiration to O2 evolves - more efficient than fermentation, glycolysis - energy becomes cheaper - multicellular life develops 4. Change in metal ion availability because of redox dependent solubility (Cu1+ insoluble but Cu2+ soluble) 5. Most species killed by O2 b/c it’s toxic
Describe stability of O2
Thermodynamically unstable but kinetically stable
Describe electron reduction of O2
1e- = thermo unfavourable. 2e- = thermo favourable (but slow and unlikely b/c requires another triplet state/ spin state change)
What state is O2 in
Triplet state (2 unpaired electrons) - not as reactive as expected
What is the stability of water
Very stable - requires lots of energy to oxidise it
What is the most reactive oxygen intermediate
Hydroxyl radical (OH)
What is the voltage difference between triplet O2 and singlet O2
Singlet O2 is one volt higher
What are the two main enzymes that deal with H20 and O2 redox reactions
PSII and cytochrome oxidase
Oxidation
Removal of electrons (associated with proton loss)
Reduction
Gain of electrons (associated with proton gain)
Redox couple
Reduced and oxidised form of one component in a redox reaction (Fe2+/ Fe3+)
Redox potential
Measure of the tendency of redox couple to donate or accept an electron (relative to the standard: hydrogen electrode)
Actual redox potential
Redox potential existing under function conditions (non-standard)
Redox potentiometry
Measurement of Em values
Key features of redox potentiometry
- Needs to show reversibility 2. Needs anaerobicity to prevent side reactions with O2 3. Needs redox mediators: chemicals that carry e- between electrodes and redox cofactor buried in protein
Em value
Conc of oxidised = conc of reduced
Delta E
Difference in Eo’ values for the 2 redox couples involved in redox reactions (measurement of Gibbs energy available from reaction)
+100 meV in joules
-9.6 kJmole-1
What usually accompanies redox reactions
Colour change
Positive delta E means..
Negative delta G
How are half reactions written
As reductions
Delta E
Eo acceptor - Eo donor
How much energy does ATP synthesis require
50 kJ/mol
Energy 1 H+ in a gradient across a membrane
-20kJ/mol = 200meV
How many protons needed to cross membrane for ATP production
At least 2.5
How much energy needed per H+ to make the proton gradient
At least 200 meV
NADH/ NAD+
n =2, Em = -320mV
O2/H20
n = 4, Em = +820mV
How many protons can be translocated across the membrane per electron
Approx. 5
What translocates protons across the membrane
Complex I, III, IV