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Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-II LH-I cytochrome c 2 ATPase cytoplasm periplasm ADP ATP h bc 1 H + H + e - Q/QH 2 /Q RC n flow in photosynthesis of cyanobacteria Electron flow in photosynthesis of purple bacteria

Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

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Page 1: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Photosynthesis 2: Energy conversion and electron conduction in soft matter

LH-II LH-I

cytochrome c2

ATPase

cytoplasm

periplasm

ADP ATP

hbc1

H+

H+

e-

Q/QH2/Q

RC

Electron flow in photosynthesis of cyanobacteria

Electron flow in photosynthesis of purple bacteria

Page 2: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

From Nature 411, (2001) 897, W. Kuhlbrandt.

Electron flow in photosynthesis of cyanobacteriaand Plants

backward direction: respiration = food consumption in mammals

Page 3: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Photosynthesis 2: Energy conversion and electron conduction in soft matter

LH-II LH-I

cytochrome c2

ATPase

cytoplasm

periplasm

ADP ATP

hbc1

H+

H+

e-

Q/QH2/Q

RC

Electron flow in photosynthesis of cyanobacteria

Electron flow in photosynthesis of purple bacteria

Page 4: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Role of Thermal Disorder on Electron Transfer in the Photosynthetic Reaction Center

Electron transfer is coupled to the thermal motion of thesurrounding protein.

Page 5: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Particle – Hole Separation in the Reaction Center and Solar Cells

proteinprotein rotated – 900 and stretched

Page 6: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

LH-II LH-I

cytochrome c2

ATPase

cytoplasm

periplasm

ADP ATP

hbc1

H+

H+

e-

Q/QH2/Q

RC

Cytochrome c2 docking

Page 7: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Photosynthetic Apparatus of Purple Bacteria

Very Large Conformational Changes

Qo

2Fe2Se-

Qo

cyt c12Fe2S cyt c1

two path-ways for oxidation of Qo site

Iron Sulfur Protein head rotationcan redirect2nd electron

Sergei Izrailev

Page 8: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Photosynthetic Apparatus of Purple Bacteria

Very Large Conformational Changes

ATP synthaseenergy transformation(proton motive force rotation)

elastomechanical coupling

rotatory catalysis(twist conformational change ATP synthesis )

F1

F1

F0

stalk

(from Wang & Oster)

(Walker, Whilce,Fillingame)www.ks.uiuc.edu

Page 9: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Photosynthetic Pathway inCyanobacteria and Plants

Page 10: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

bacterio-chlorophyll

bacterio-pheophytin

ubiquinone

Electron Carrying Molecules

chain

chain

chain

Page 11: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Particle – Hole Separation in the Reaction Center and Solar Cells

proteinprotein rotated – 900 and stretched

Page 12: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

energy gap

energy gap

The energy gap is Gaussian distributed

Page 13: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Two State QM System Coupled to Protein Matrix

Hamiltonian

Protein matrix is a bath of oscillators linearlycoupled to the electron transfer according to

only a single oscillator considered at present!

First case: Coupling to a single oscillator

Page 14: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Hamiltonian

Protein matrix is a bath of oscillators linearlycoupled to the electron transfer according to

Two State QM System Coupled to Protein Matrix

Second case: Coupling to an ensemble of oscillators

Page 15: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Electron Transfer Process Coupled to the Protein Matrix

Rate for an ensemble of oscillators

But we don’t know all the coupling constants cj ? All we need to know is

Relaxation rate

Page 16: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Solution of Rate Equation

Page 17: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Electron Transfer Process Coupled to the Protein Matrix

Rate for an ensemble of oscillators

But we don’t know all the coupling constants cj ? All we need to know is

Relaxation rate

Page 18: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Electron Transfer Process Coupled to the Protein Matrix

Relaxation rate

energy gap correlation functionenergy gap

rms deviation of energy gap

1994

Page 19: Photosynthesis 2: Energy conversion and electron conduction in soft matter LH-IILH-I cytochrome c 2 ATPase cytoplasm periplasm ADPATP h bc 1 H+H+ H+H+

Temperature Dependence of Electron Transfer Rate