Johnson (Photosynthesis) Flashcards
How does photosynthesis power biosphere?
- source of all food, O and most energy (≈88%)
How did photosynthesis change the world?
increase in atmospheric O2 conc allowed multicellular organisms to appear
- spike in [O2] is coniferous period
- many trees etc. died and prod fossil fuels present today
- at this time plants also dev lignin in cell walls
Why is ps the basis of food chain?
- virtually all life depends on it to provide energy in form of red C molecules
What are the types of photosynthetic organism, and eg.s?
- euk oxygenic ps (chloroplasts) = eg. plants, mosses
- prok oxygenic ps = eg. cyanobacteria (-)
- prok anoxygenic ps = eg. purple bacteria (-)
- archaeal ps = halobacteria
Where does photosynthesis take place in euks?
- chloroplast thylakoid membrane
How is thylakoid membrane specialised for photosynthesis?
- highly folded
- providing huge area for light absorption and e- transport
How does oxygenic photosynthesis occur in plants?
- e- transport in thylakoid membrane
- enzymatic machinery responsible for CO2 fixation located in stroma
- main aldehyde product is glyceraldehyde-3-phosphate
- light and ‘dark’ reactions
Are dark reactions really in the dark?
- no, only occur in light
- ie, don’t cont if remove light after ATP and NADPH formed
What is the photosynthetic e- transfer (PET) chain?
- 2 light driven reactions in chlorophyll-protein complexes PSII and PSI
- result in e- transfer via chain of acceptors from water to NADP+, w/ O formed as by product
- e- transfer coupled to pmf formation for ATP synthesis
- none of complexes pump protons, all translocate
- NADPH/NADP+ has v -ve redox pot and H2O/O2 v +ve
- H+ released into lumen
What does it mean to say complexes translocate protons instead of pumping them?
- get net redistribution by performing reactions on both sides of membrane
What is the function of photosystems?
- carry out light dep e- transfer
What is the structure of photosystems?
2 parts:
- reaction centre = where photochemical redox reactions take place
- light harvesting antenna system = responsible for light absorption and transfer of captured light energy to reaction centre
What is the key light absorbing pigment molecule in both structures of photosystems, and how is it bound?
- chlorophyll
- non covalently bound to these proteins
What is the basic structure of photosystems?
- antenna complex formed of 100s of chlorophylls
- transfer absorbed light energy to special pair chlorophylls of reaction centre that are redox active
What do antenna chlorophylls transfer?
- energy, NOT e-s
What 2 parts is chlorophyll formed of?
- tetrapyrrole ring = similar to haem, but coords Mg2+
- hydrophobic phytyl tail region
What is the conjugated π e- system in tetrapyrrole ring of chlorophyll responsible for?
- light absorption
- when chlorophyll absorbs light, e- in this region promoted to higher energy level
What occurs in the reaction centre chlorophyll molecules, and how does this vary between PSI and PSII?
- 1° donor oxidised upon excitation
- -> P680 for PSII
- -> P700 for PSI
- e- transferred to acceptor, which is red
- -> lipid soluble plastoquinone for PSII
- -> soluble protein ferredoxin for PSI
- 1°donor re-red by 2°donor
- -> H2O for PSII
- -> plastocyanin for PSI
What is the redox ‘Z-scheme’ for photosynthesis?
- light energy used by reaction centres to drive +ΔG reactions that transfer e-s from donor w/ +ve redox pot (water) to acceptor w/ more -ve redox pot (NADP+)
What occurs in PSII?
- uses light energy to transfer e-s from special pair P680 to lipid soluble PQ
- P680+ drives splitting of water into e-, H+ and O2 (photolysis) by Mn cluster attached to PSII
- protons released into lumen, while 2e-s used to red P680+ to P680
- once red, PQ binds 2H+ from stroma side of membrane
What is the overall reaction in PSII?
- H2O + PQ + 2H+stroma –> 1/O2 + PQH2 + 2H+lumen
What occurs in cytochrome b6f?
- similar to complex III in mito
- carries out Q cycle
What is the Q cycle?
- complex series of reactions that ox PQ and transfer e- to plastocyanin, a small soluble e- transfer protein located on lumen side of thylakoid membrane
What is the overall Q cycle reaction?
- PQH2 + 2PCox + 2H+stroma –> 2PCred + 4H+lumen
What occurs in PSI?
- uses light energy to transfer e-s from special pair P700 to ferredoxin
- P700+ drives ox of plastocyanin (PC) on lumen side of membrane regen P700
What is ferredoxin?
- small soluble protein on stroma side of thylakoid membrane
What is the overall reaction is PSI?
- PCred + Fdox —-light—> PCox + Fdred
What is plastocyanin?
- small soluble e- transfer protein
What is the role of plastocyanin?
- Cu ion bound at active site coord by several His residues and acts as e- carrier
- Cu ox from Cu+ –> Cu2+ by PSI and red back to cytochrome b6f
What is the role of ferredoxin?
- binds 2Fe-2S cluster at active site
- bound by several Cys residues that act as e- carrier
What occurs in ferredoxin-NADP+ reductase?
- contains FAD cofactor which sequentially ox 2 molecules of Fd
- then uses e-s to red NADP+ –> NADPH, w/ H+ taken up from stroma
What is the overall reaction in ferredoxin-NADP+ reductase?
- 2Fdred + NADP + H+stroma –> 2Fdox + NADPH
Are the structures of chloro and mito ATPases similar?
- v similar
What is the difference between chloro and mito ATPases?
- stoichiometry of H+ of ATP much higher in chloro
- 14 c subunits, instead of 8
What is the overall reaction in CF1CF0 ATPase?
- 14H+lumen + 3Pi + 3ADP –> 14H+stroma + 3ATP + 3H2O
What is the meaning of Jablonski diagrams?
- molecules only absorb photons w/ energy equal to energy gap between e- orbitals
What are the diff excitation states in Jablonski diagrams?
- S0 = ground state
- S1 = 1st excited state
- S2 = 2nd excited state
How do red and blue photons vary in terms of Jablonski diagrams?
- red photons match S0 -> S1 energy gap
- blue photons match S0 -> S2 energy gap
- red are higher energy photons w/ lower wavelength
What timescale does light absorption occur on?
- femtosecond (10^-15)
What do electronic, vibrational and rotational energy levels show?
- some energy levels more favourable
Does photosynthesis need green light, and why?
- yes, underneath leaf
- as chloroplasts filter out all blue and red light, so green req
What is the fate of S2 excited state, and timescale?
- e- v rapidly loses part of absorbed energy as heat internal conversion
- falls to S1 state
- picosecond timescale (10^-12)
What are fates of S1 excited state, and timescales?
- slower, nanosecond (10^-9), process as closer to nucleus so lower energy and excited state more stable
- internal conversion to S0 slow enough that fluorescence can compete as alt channel of de-excitation
- if another chlorophyll in close prox then FRET
How does energy transfer occur between chlorophylls, and when can this happen?
- FRET
- excited energy transferred from excited donor chlorophyll to acceptor chlorophyll in ground state
- can occur when 2 chlorophylls in close prox and have overlapping excited state energy levels
- keep flipping around and energy cascades between them
How is FRET distance dep?
- efficiency varies w/ 6th power of distance
- ie, if distance between donor and acceptor doubles, FRET transfer time increases 64x
- ∴ only efficient over short distances
Why are antenna needed?
- increase reaction centre rate by 2 orders of magnitude
- acts to capture and concentrate light energy
What features should antenna have?
- high as poss pigment conc
- wide spectral cross section (as many colours as poss)
- wide spatial cross section
- modularity build up in low light, red in high light (don’t need as many antenna complexes in high light as more excitation)
- provide directionality to energy transfer
- min losses of excitation energy to heat and fluorescence, and prevent e- transfer
Why is there a pigment variety in plants?
- variation in length of conjugated π e- system affects wavelength of light absorbed by each pigment
What is the pigment absorption spectra?
- combo of multiple pigment types in antenna broadens spectral cross section of light energy that is absorbed and transferred to RC chlorophylls
What pigments are bound to antenna proteins, and how?
- antenna proteins non covalently bind pigments at v high conc to ensure efficient light absorption
- LHCII 1 of most abundant membrane proteins
What is the antenna structure of PSII?
- multiple antenna proteins provide large spatial cross section for light absorption
- ≈ 157 chlorophylls/RC
- PSII forms dimeric supercomplex = 1x LHCII trimer per RC, 2x PSII, 2x LHCII monomers per RC and O evolving complex (catalyst)
What is the antenna complex of PSI?
- generally don’t have dimers
- multiple antenna proteins provide large spatial cross section for light absorption
- ≈155 chlorophylls/RC
- PSI RC and 4 x LHCI monomers per RC
What makes the structure of antenna modular?
- can build up or down
What is the modular structure of antenna?
- leaves –> thylakoid membranes –> solubilisation of membranes in detergent –> separation of sucrose grad ultracentrifugation
- [LHCII] increases in low light and decreases in high light