Chapter 15 (part1)

Photosynthesis

Implications of

Photosynthesis on

Evolution

• Energy metabolism• Carbohydrate metabolism• Amino acid metabolism• Lipid Metabolism• Nucleic acid metabolism• Oxygen toxicity

Implications of Photosynthesis on

Biochemistry?

The Sun - Ultimate Energy

• 1.5 x 1022 kJ falls on the earth each day

• 1% is absorbed by photosynthetic organisms and transformed into chemical energy

• 6CO2 + 6H2O C6H12O6 + 6O2

• 1011 tons (!) of CO2 are fixed globally per year

• Formation of sugar from CO2 and water requires energy

• Sunlight is the energy source!

Photosynthesis: Light Reactions and Carbon

Fixation• The light reactions capture light energy and

convert it to chemical energy in the form of reducing potential (NADPH) and ATP with evolution of oxygen

• During carbon fixation (dark reactions) NADPH and ATP are used to drive the endergonic process of hexose sugar formation from CO2 in a series of reactions in the stroma

Light: H2O + ADP + Pi + NADP+ + light O2 + ATP + NADPH + H+

CF: CO2 + ATP + NADPH + H+ Glucose + ADP + Pi + NADP+

Sum: CO2 + light Glucose + O2

Chloroplast• Inner and outer membrane = similar to

mitochondria, but no ETC in inner membrane.• Thylakoids = internal membrane system.

Organized into stromal and granal lammellae.• Thylakoid membrane - contains

photosynthetic ETC• Thylakoid Lumen – aqueous interior of

thylkoid. Protons are pumped into the lumen for ATP synthesis

• Stroma – “cytoplasm” of chloroplast. Contains carbon fixation machinery.

• Chloroplasts possess DNA, RNA and ribosomes

Conversion of Light Energy to Chemical Energy

• Light is absorbed by photoreceptor molecules (Chlorophylls, carotenoids)

• Light absorbed by photoreceptor molecules excite an electron from its ground state (low energy) orbit to a excited state (higher energy) orbit .

• The high energy electron can then return to the ground state releasing the energy as heat or light or be transferred to an acceptor.

• Results in (+)charged donor and (–)charged acceptor = charge separation

• Charge separation occurs at photocenters. • Conversion of light NRG to chemical NRG

Photosynthetic Pigments

Chlorophyll• Photoreactive,

isoprene-based pigment • A planar, conjugated

ring system - similar to porphyrins

• Mg in place of iron in the center

• Long chain phytol group confers membrane solubility

• Aromaticity makes chlorophyll an efficient absorber of light

• Two major forms in plants Chl A and Chl B

Accessory Pigments

• Absorb light through conjugated double bond system • Absorb light at different wavelengths than Chlorophyll• Broaden range of light absorbed

Carotenoid

Phycobilin

Absorption Spectra of Major Photosynthetic

Pigments

Harvesting of Light and Transfer of Energy to

Photosystems• Light is absorbed by

“antenna pigments” and transferred to photosystems.

• Photosystems contain special-pair chlorophyll molecules that undergo charge separation and donate e- to the photosynthetic ETC

Resonance Transfer• Energy is transfer through antenna

pigment system by resonance transfer not charge separation.

• An electron in the excited state can transfer the energy to an adjacent molecule through electromagnetic interactions.

• Acceptor and donor molecule must be separated by very small distances.

• Rate of NRG transfer decreases by a factor of n6 (n= distance betwn)

• Can only transfer energy to a donor of equal or lower energy

Photosynthetic Electron Transport and

Photophosphorylation • Analogous to respiratory ETC and oxidative

phosphorylation

• Light driven ETC generates a proton gradient which is used to provide energy for ATP production through a F1Fo type ATPase.

• The photosynthetic ETC generates proton gradient across the thylakoid membrane.

• Protons are pumped into the lumen space.

• When protons exit the lumen and re-enter the stroma, ATP is produced through the F1Fo ATPase.

Photosynthetic ETC

Eukaryotic Photosystems

• PSI (P700) and PSII (P680) • PSI and PSII contain special-pair

chlorophylls• PSI absorbs at 700 nm and PSII absorbs

at 680 nm • PSII oxidizes water (termed “photolysis") • PSI reduces NADP+ • ATP is generated by establishment of a

proton gradient as electrons flow from PSII to PSI

Z-Scheme

Terminal Step in Photosynthetic ETC

• Electrons are transferred from the last iron sulfur complex to ferredoxin.

• Ferredoxin is a water soluble protein coenzyme

• Very powerful reducing agent.

• Ferredoxin is then used to reduce NADP+ to NADPH by ferredoxin-NADP+ oxidoreductase

• So NADP+ is terminal e- accepter

The Z Scheme• An arrangement of the electron

carriers as a chain according to their standard reduction potentials

• PQ = plastoquinone • PC = plastocyanin • "F"s = ferredoxins

• Ao = a special chlorophyll a

• A1 = a special PSI quinone

• Cytochrome b6/cytochrome f complex is a proton pump

P680(PSII) to PQ Pool

Electrons are passed from Pheophytin to Plastoquinone

• Plastoquinone is analagous to ubiquinone

• Lipid soluble e- carrier• Can form stable semi-

quinone intermediate• Can transfer 2

electrons on at a time.

Transfer of e- from PQH2 to Cytbf Complex (another Q-

cycle)• Electrons must be transferred one at a time to Fe-S group.

• Another Q-cycle• First PQH2 transfers one

electron to Fe-S group, a PQ- formed. 2 H+ pumped into lumen

• A second PQH2 transfers one electron to Fe-S group and the one to reduce the first PQ- to PQH2. 2 more H+ pumped into lumen

• 4 protons pumped per PQH2. Since 2 PQH2 produced per O2 evolved 8 protons pumped

Excitation, Oxidation and Re-reduction of

P680• Special pair

chlorophyll in P680 (PS II) is excited by a photon

• P680* transfer energy as a e- to pheophytin A through a charge separation step.

• The oxidized P680+ is re-reduced by e- derived from the oxidation of water

Oxygen evolution by PSII

• Requires the accumulation of four oxidizing equivalents

• P680 has to be oxidized by 4 photons

• 1 e- is removed in each of four steps before H2O is oxidized to O2 + 4H+

• Results in the accumulation of 4 H+ in lumen

Kristina N. Ferreira, Tina M. Iverson, Karim Maghlaoui, James Barber, and So IwataScience 19 March 2004: 1831-1838.