In the 1940s, Robert Emerson and his colleagues at the University of Illinois discovered that two separate

photoreactions are involved in oxygenic photosynthesi

. Initially, they observed a dramatic drop in photosynthesis rate above a wavelength of about 690 nm.
This seemed odd to them because Chlorella contains chlorophyll molecules that strongly absorb light at
wavelengths above 690 nm.
Indeed, they discovered that photosynthesis driven by a combination of long and short wavelengths of red light
exceeded the sum of activities obtained with either wavelength alone. This synergistic phenomenon became
known as the Emerson enhancement effect.
We now know that the Emerson enhancement effect is the result of two distinct photosystems working together
in series. Photosystem I (PSI) has an absorption maximum of 700 nm, whereas photosystem II (PSII) has an
absorption maximum of 680 nm. Each electron that passes from water to must be photoexcited twice, once by
each photosystem. When illumination is restricted to wavelengths above 690 nm, PSII is not active, and
photosynthesis is severely impaired.
PHOTO TRANSDUCTION I
The first stage of photosynthetic energy transduction is the capture of light energy from the sun. As with
all electromagnetic radiation, light has both wave-like and particle-like properties. The portion of the
electromagnetic spectrum visible to us, for example, consists of light having wavelengths ranging from
about 380 to 750 nm. However, light also behaves as a stream of discrete particles called photons, each
photon carrying a quantum (indivisible packet) of energy. The wavelength of a photon and the precise
amount of energy it carries are inversely related
When a photon is absorbed by a pigment (light absorbing molecule), such as chlorophyll, the energy of
the photon is transferred to an electron, which is energized from its ground state in a low-energy orbital
to an excited state in a high-energy orbital. This event, called photoexcitation, is the first step in
photosynthesis. Because each pigment has a different configuration of atoms and electrons, pigments
display characteristic absorption spectra that describe the particular wavelengths of light absorbed by a
pigment. The absorption spectra of several common pigments found in photosynthetic organisms, along
with the spectrum of solar
PHOTO TRANSDUCTION II
uses a series of electron carriers to transport excited electrons from chlorophyll to the coenzyme
nicotinamide adenine dinucleotide phosphate NADP+ , forming NADPH, the reduced form of NADP+. This
process is known as photoreduction and involves a chloroplast electron transport system (ETS)
The light-harvesting complex (or antenna complex; LH or LHC) is
an array of protein and chlorophyll molecules embedded in the
thylakoid membrane of plants and cyanobacteria, which
transfer light energy to one chlorophyll a molecule at the
reaction center of a photosystem
When P680 absorbs a photon, it gets excited to P680*. This excited state has much lower redox potential, meaning it can
donate an electron easily.
Photon hits PSII → excites P680 → becomes P680*
Now P680* is energized and becomes a strong reducing agent (E° ≈ −0.8 V).
It donates 1 electron to pheophytin → then to plastoquinone eventually.
P680 becomes P680⁺ (oxidized)
 Now it’s missing 1 electron and has very high redox potential (E° ≈ +1.2 V).
 This makes P680⁺ extremely hungry for an electron.
Now PSII pulls an electron from water
 P680⁺ pulls an electron from the Oxygen-Evolving Complex (OEC) (aka the Mn₄Ca cluster).
 The OEC extracts electrons from water, one at a time, to replace the ones lost by P680.
 One positive charge (P680⁺)
 One negative charge (Ph⁻)
 This is crucial because it:
 Keeps the electron moving forward down the electron transport chain.

• One positive charge (P680⁺)
• One negative charge (Ph⁻)
• This is crucial because it:
• Keeps the electron moving forward down the
electron transport chain.
• Triggers water splitting to replace the lost electron in
P680⁺.

• Photosystem II (PSII) and Photosystem I (PSI) absorb light and

drive the movement of electrons from water to NADP⁺.
• Each electron needs to be excited twice: once in PSII and
once in PSI.
• Each excitation requires one photon.
• So to recap the timing:
• Photon excites P680 → P680* P680 is absorbing energy.
• P680* donates 1 e⁻ → becomes P680⁺
• P680⁺ pulls e⁻ from OEC → OEC takes e⁻ from H₂O via Oxygen-Evolving
Complex (OEC) (aka the Mn₄Ca cluster).
• Water gives 4 electrons total (from 2 H₂O → 4H⁺ + 4e⁻ + O₂).
• But these are extracted one at a time over 4 cycles of photon hits at PSII.
• The OEC stores oxidative "power" until it’s ready to release O₂ after 4 hits.
 • So to recap the timing:
• Photon excites P680 → P680* P680 is absorbing energy.
• P680* donates 1 e⁻ → becomes P680⁺
• P680⁺ pulls e⁻ from OEC → OEC takes e⁻ from H₂O via Oxygen-Evolving Complex (OEC) (aka the Mn₄Ca
cluster).
• Water gives 4 electrons total (from 2 H₂O → 4H⁺ + 4e⁻ + O₂).
• But these are extracted one at a time over 4 cycles of photon hits at PSII.
• The OEC stores oxidative "power" until it’s ready to release O₂ after 4 hits.
E = hc/λ
([(6.626 × 10 -34 J ∙ s)(3.00 × 108 m/s)])/((7.00 × 10 -7 m)) = 2.84 × 10−19 J
An einstein of light is Avogadro’s number of photons (6.022 × 1023 ); thus the energy of one einstein of photons at 700 nm is given
(2.84 × 10−19 J/photon)(6.022 × 1023 photons/einstein)
= 17.1 × 104 J/einstein
= 171 kJ/einstein
So, a “mole” of photons of red light has about five times the energy needed to produce a mole of ATP from ADP and Pi (30.5 kJ/mo
ΔG = 2.3RT ΔpH + ZF Δψ =−17 kJ/mol
E = hc/λ
= 2.84 × 10−19 J
An einstein of light is Avogadro’s number of photons (6.022 × 1023 ); thus the energy of one einstein of photons at 700 nm is
given by
(2.84 × 10−19 J/photon)(6.022 × 1023 photons/einstein)
= 17.1 × 104 J/einstein
Becker World of the cell 8th ed p 306
2 H₂O → Mn₄CaO₅ → TyrZ → P680⁺ → Pheophytin → QA → QB
→ PQ → Cyt b₆f → PC → PSI
Next the electron is passed to QA , a plastoquinone that is tightly bound to protein D2 (Figure 11-9).
Plastoquinone is similar to coenzyme Q, a component of the mitochondrial electron transport system (see
Figure 10-15). Another plastoquinone, QB , receives two electrons from and picks up two protons from the
stroma, thereby becoming reduced to plastoquinol QBH2, . It then enters a mobile pool of QBH2 in the
interior lipid phase of the photosynthetic membrane. can then pass two electrons and two protons
cytochrome b6/f to the cytochrome complex as it is oxidized back to . Because a chlorophyll molecule
transfers one electron per photon absorbed, the formation of one mobile plastoquinol molecule depends on
two sequential photoreactions at the same reaction center:
2 photons + QB + 2H+stroma + 2e- → QBH2
To replace the electron lost to plastoquinone, oxidized is reduced by an electron obtained from water. To do this, PSII includes
an oxygen-evolving complex (OEC), an assembly of proteins and manganese ions that catalyzes the splitting and oxidation of
water, producing molecular oxygen , electrons, and protons. Two water molecules donate four electrons, one at a time by way
of a tyrosine residue on protein D1, to four molecules of oxidized P680+ (see Figures 11-8 and 11-9). A manganese-stabilizing
protein (MSP) holds a cluster of four manganese ions that serve to accumulate the four electrons released as the two water
molecules are oxidized. This prevents the formation of partly oxidized intermediates, such as hydrogen peroxide (H2O2) or
superoxide anion , that can be toxic to the cell if released. In the process, four protons and one oxygen molecule are released
within the thylakoid lumen as shown here: 2H2O → O2 + 4e- + 4H+ lumen

The protons accumulating in the lumen contribute to an electrochemical proton gradient

across the thylakoid membrane, and the oxygen molecule diffuses out of the chloroplast.
Because the complete oxidation of two water molecules to molecular oxygen depends on
four photoreactions, the net reaction catalyzed by four photoexcitations at PSII can be
summarized by doubling Reaction and adding it to Reaction :
4 photons + 2H2O + 2QB + 4H+ stroma O2 + 2QBH2 + 4H (11-5) + lumen
Note that the protons removed from the stroma are actually still in transit to the lumen as part of ,
while the protons added to the lumen at this point are derived from oxidation of water. The light-
dependent oxidation of water to protons and molecular oxygen, called water photolysis, is believed
to have appeared in cyanobacteria between 2 and 3 billion years ago, thereby permitting
exploitation of water as an abundant electron donor. The oxygen released by the process
dramatically changed the Earth’s early atmosphere, which did not originally contain free oxygen,
and allowed the development of aerobic respiration.
Note that the protons removed from the stroma are actually still in transit to the lumen as part of ,
while the protons added to the lumen at this point are derived from oxidation of water. The light-
dependent oxidation of water to protons and molecular oxygen, called water photolysis, is believed to
have appeared in cyanobacteria between 2 and 3 billion years ago, thereby permitting exploitation of
water as an abundant electron donor. The oxygen released by the process dramatically changed the
Earth’s early atmosphere, which did not originally contain free oxygen, and allowed the development of
aerobic respiration. Becker 8th edition 306 onward
Two photons excite two electrons through PSI (cyclically),
• And that powers the production of one extra ATP, without making NADPH.
• Each pair of electrons that goes through this cyclic path is estimated to move
~4 protons across the thylakoid membrane.
o Some estimates say 2–4 protons per 2 electrons, depending on species and
conditions.
o Let’s use 4 H⁺ per 2e⁻ as a good working estimate (widely accepted for CEF).
To make one molecule of glyceraldehyde-3-phosphate (G3P) in the
Calvin cycle, the plant needs:
• 6 NADPH
• 9 ATP
Each NADPH is made by the reduction of NADP⁺, which requires 2
electrons.
So, to make 6 NADPH, you need:
6 NADPH × 2 electrons = 12 electrons
Each electron:
• Gets excited once at PSII (to move through the
electron transport chain and pump protons for ATP).
• Then gets excited again at PSI (to reduce NADP⁺ to
NADPH).
So:
Each electron = 2 photons (1 for PSII, 1 for PSI)
12 electrons × 2 photons = 24 photons
12 photons at PSII excite 12 electrons
1 water molecule provides 2 electrons
So to get 12 electrons, we need: 6 H₂O molecules split → 12 e⁻ + 12 H⁺ + 3 O₂
What happens to the 12 electrons?
hey travel through:
• Plastoquinone (PQ)
• Cytochrome b6f (Q-cycle)
• Plastocyanin
• Then to Photosystem I (needs another 12 photons)
• Q-cycle pumps 4 H⁺ per pair of electrons
• 12 electrons = 6 pairs → 6 × 4 = 24 H⁺ pumped
✅ So now total protons in the thylakoid lumen:
• 12 H⁺ (from water splitting)
• 24 H⁺ (from Q-cycle)
→ 36 H⁺ total
4/4.5H+ = 1ATP
Two photons excite two electrons through PSI (cyclically),
• And that powers the production of one extra ATP, without
making NADPH.
• Each pair of electrons that goes through this cyclic
path is estimated to move ~4 protons across the thylakoid
membrane.
o Some estimates say 2–4 protons per 2 electrons,
depending on species and conditions.
o Let’s use 4 H⁺ per 2e⁻ as a good working estimate
(widely accepted for CEF).