Lecture 44:

Photosynthesis and Redox

NO NO YES
In eukaryotes, photosynthesis
occurs in chloroplasts
The major steps of photosynthesis
• Photon absorption excites an electron
– Described in lectures 28 and 29
• Electron flow allows H+ to be pumped into a
region of high concentration/positive charge
– Focus of this lecture
• H+ flow out of the high concentration/positive
charge region drives ATP synthesis
– Focus of Monday’s lecture
• ATP is used to power carbon fixation, generating
e.g. sugars
– Maybe next year?
The major steps of photosynthesis

Monday

Today
 The photosynthesis
electron transport chain
Why do electrons flow this way?
 Outline for today’s lecture
• Photosynthesis
– Overview and some cellular context
– The photosynthesis electron transport chain
• Reduction and oxidation
– Terminology
– Role of electric potential
– Predicting net direction of electron flow
• Coupling of electron flow to H+ “pumping”
– H+ production from water splitting
– The “Q cycle” mechanism
 First, some key terminology:
reduction and oxidation
• Reduction is the gain of an electron. Oxidation
is the loss of an electron.
• The nomenclature reflects the tendency of
oxygen, a highly electronegative atom, to
partially or fully steal e- from other molecules.

O2
e-
 First, some key terminology:
reduction and oxidation
• Reduction is the gain of an electron. Oxidation
is the loss of an electron.
• Whenever one molecule is oxidized, another is
reduced (unless the e- is truly liberated).
• The oxidized and reduced forms of a molecule
constitute a redox pair.

reduced oxidized
form form
 First, some key terminology:
reduction and oxidation
• Reduction is the gain of an electron. Oxidation
is the loss of an electron.
• When a molecule in water is reduced, it often
picks up a H+, too:

• Adding/removing a net hydrogen (H+ & e-) is

called hydrogenation/dehydrogenation
 First, some key terminology:
reduction and oxidation
• Fun fact: hydrogenation of fatty acids is used
to make margarine
 First, some key terminology:
reduction and oxidation
• To understand the net direction of electron
flow in the photosynthesis electron transport
chain, we would like to know:
• What is the change in energy associated with
a balanced redox reaction?, e.g.
Electron flow and electric potential

Electrons can decrease their electric potential energy

Ue by moving to molecules where they experience a
more positive electric potential F
Electrons experience electric potentials
inside molecules

Thorium nucleus Oxygen nucleus

(90 protons) (8 protons)
ro ns ?!
ct
h er ele
97 ot
Electrons can minimize their electric potential energy
Ue by moving to molecules where they experience a
more positive electric potential F

We can measure relative values of F experimentally.

Electron flow between molecules, driven by
electric potential differences, can be
measured

Metal #1 Metal #2
Electrons flow to molecules with more
positive internal electric potentials
Magnesium Graphite
 Measuring “reduction potential” of
biological redox pairs
The previous examples used the same
solution in both cells but different
electrode types. Now suppose we use
identical electrodes, but different
solutions.

Electrons will flow toward the solution

containing the “greedier” redox pair.

We can use this electron flow to

measure the electrical potential of a
solution relative to a standard: we call
this the “reduction potential”.
 What will happen if Aoxidized has a higher affinity
for electrons than H+?

?
The electric
potential on
the left is
more positive
(reduction
potential is
positive)
 What will happen if Aoxidized has a
lower affinity for electrons than H+?

The electric ?
potential on
the left is less
positive
(reduction
potential is
negative)
Reduction potential Eo
 Reduction potentials along the
photosynthesis electron transport chain
 Relationship between reduction potential
and energy differences

E0’ = - 400 mV

E0’ = - 320 mV

What is the change in electric potential energy DUe on transferring

two electrons from ferredoxin (Fd2-) to NADP+ at standard state?
Question 2: How is H+ “pumping” driven
by electron flow?
Proton “pumping” mechanism

The Expectation The Reality

H production from water splitting
+
Photosynthesis and aerobic respiration
Plastoquinone (Q) as a “proton pump”

Photosystem II Cytochrome b6-f

(initial site of complex
excitation)
Plastoquinone (Q) as a “proton pump”

Photosystem II Cytochrome b6-f

(initial site of complex
excitation)
Plastoquinone (Q) as a “proton pump”

Photosystem II Cytochrome b6-f

(initial site of complex
excitation)
Plastoquinone (Q) as a “proton pump”

Cytochrome b6-f
complex
Plastoquinone (Q) as a “proton pump”

Cytochrome b6-f
complex
Plastoquinone (Q) as a “proton pump”

Cytochrome b6-f
complex
Plastoquinone (Q) as a “proton pump”

Cytochrome b6-f
complex
 Plastoquinone (Q) as a “proton pump”

This clever
recycling of
electrons in a loop Cytochrome b6-f
is called the
complex
“Q cycle”
Electron transport chains in photosynthesis
and respiration both use Q cycles
 What we hope you learned today
• How a H+ gradient is generated during
photosynthesis
– Why electrons move down an electron transport
chain from carrier to carrier
– How electron movement is coupled to proton
“pumping” in the Q cycle
• How to describe redox reactions
• How to build a battery