CHAPTER 21 Photosynthesis

21-1 What Are the General Properties of Photosynthesis?

 Photosynthesis Occurs in Membranes
1. in photosynthetic eukaryotes, the photosynthetic membranes are localized in large organelles
known as chloroplasts (葉綠體)
2. Chloroplasts are one member in a family of related plant-specific organelles known as plastids
3. Photosynthesis occurs in thylakoid membranes of chloroplasts, structure involving paired folds that
stack to form grana (葉綠餅)
4. Granum(葉綠餅) may contain dozens of thylakoid vesicles (類囊體), and are joined by lamellae that
run through the soluble portion, stroma (基質)
5. Chloroplasts thus possess three membrane-bound aqueous compartments: the intermembrane
space, the stroma, and the interior of the thylakoid vesicles, the so-called thylakoid space
6. The thylakoid membrane has a highly characteristic lipid composition and, like the inner membrane
of the mitochondrion, is impermeable to most ions and molecules
7. Chloroplasts posses DNA, RNA and ribosomes

 Photosynthesis Consists of Both Light Reactions and Dark Reactions.

1. The light reactions of photosynthesis, of which O2 evolution is only one part, are associated with
the thylakoid membranes
2. dark reactions, notably CO2 fixation, are located in the stroma
3. radiant electromagnetic energy (light) is transformed by photochemical system located in the
thylakoids to yield chemical energy in the form of NADPH and ATP
4. NADPH and ATP can then be used to drive the endergonic process of hexose formation from CO2 by
a series of enzymatic reactions found in the stroma
 Water Is the Ultimate e- Donor for Photosynthetic NADP+ Reduction
1. Light energy is necessary to make the unfavorable reduction of NADP+ by H2O
2. 12 NADPH + 12 H+ + 18 ATP + 6 CO2 + 11 H2O → glucose-1-P + 12 NADP+ + 18 ADP + 17 Pi
3. In photosynthetic bacteria H2S isopropanol, or some similar oxidizable substrate
21-2 How Is Solar Energy Captured by Chlorophyll?
 Chlorophylls and Accessory Light-Harvesting Pigments Absorb Light of Different Wavelengths
1. Photosynthesis depends on the photoreactivity of chlorophyll
2. Chlorophylls are magnesium-containing substituted tetrapyrroles
3. The structures of chlorophyll a and b
4. Chlorophylls are excellent light absorbers because of their aromaticity (𝜋 electrons above and
below the planar ring structure)
5. When light energy is absorbed, an electron is promoted to a higher orbital, enhancing the potential
for transfer of this electron to a suitable acceptor

6. chlorophylls a and b can harvest a wider spectrum of incident energy

7. accessory light-harvesting pigments, increase the possibility for absorption of incident light of
wavelengths not absorbed by the chlorophylls
8. Carotenoids (類胡蘿蔔素)and phycocyanobilins(藻膽素), like chlorophyll, possess many conjugated
double bonds and thus absorb visible light
 The Light Energy Absorbed by Photosynthetic Pigments Has Several Possible Fates
1. Each photon represents a quantum of light energy. A quantum of light energy absorbed by a
photosynthetic pigment has four possible fates
 Loss as heat
 Loss as light
 Resonance energy transfer
 Energy transduction
 Photosynthetic Units Consist of Many Chlorophyll Molecules but Only a Single Reaction Center
1. The transduction of light energy into chemical energy involves oxidation–reduction
2. Chlorophyll involved in light harvesting and the transfer of light energy to photoreactive sites by
 exciton transfer, and it participates directly in the photochemical events whereby light energy
becomes chemical energy
3. A photosynthetic unit can be envisioned as an antenna of several hundred light-harvesting
chlorophyll molecules (green) plus a special pair of photochemically reactive chlorophyll a molecules
called the reaction center
4. Route：one to the other → reaction canter (occur photochemical event)

21-3 What Kinds of Photosystems Are Used to Capture Light Energy?

 Chlorophyll Exists in Plant Membranes in Association with Proteins
1. Cyanobacteria, green algae, and higher plants are oxygenic phototrophs (contain PSI and PSII)
2. Photosynthesis bacteria only one photosystem, cannot use light to split water and release O2
3. Oxygenic phototrophs have two distinct photosystems: photosystem I (PSI) and photosystem II (PSII)
4. PSI is defined by reaction center chlorophylls with maximal red light absorption at 700 nm
5. PSII uses reaction centers that exhibit maximal red light absorption at 680 nm
6. Both P700 and P680 are chlorophyll a dimers situated within specialized protein complexes
 PSI and PSII Participate in the Overall Process of Photosynthesis
1. PSI provides reducing power in the form of NADPH
2. PSII splits water, producing O2, and feeds the electrons released into an electron-transport chain
that couples PSII to PSI
3. Electron transfer between PSII and PSI pumps protons for chemiosmotic ATP synthesis
4. electrons flow from H2O to NADP1, driven by light energy absorbed at the reaction centers
5. Oxygen is a by-product of the photolysis, literally“light-splitting,” of water
6. Accompanying electron flow is production of a proton gradient and ATP synthesis (photo-
phosphorylation)
 The Pathway of Photosynthetic Electron Transfer Is Called the Z Scheme
1. The various electron carriers：
 Mn complex symbolizes the manganese-containing oxygen-evolving complex
 QA and QB represent special plastoquinone molecules
 PQ, the plastoquinone pool
 PC is the immediate e- donor to P700+
 Fd is the soluble ferredoxin pool that serves as the e- donor to the flavoprotein (Fp), called
ferredoxin–NADP+ reductase → which catalyzes reduction of NADP+ to NADPH
2. Overall photosynthetic electron transfer is accomplished by three membrane-spanning
supramolecular complexes (PSII、cytochrome b6 f complex、PSI)
 3. The PSII complex is as a light-driven water:PQ oxidoreductase, which can photolysis of water
(oxygen-evolving complex, or OEC)
4. PSII possesses a metal cluster containing 4 Mn atoms, Ca atom, O atoms, and Cl-

 Oxygen Evolution Requires the Accumulation of Four Oxidizing Equivalents in PSII

1. P680 reaction center complex cycles through five different oxidation states, numbered S0 to S4
2. One electron and one proton are removed photochemically in each step
3. When S4 is attained, an O2 molecule is released as PSII returns to oxidation state S0 and two new
water molecules bind
 Electrons Are Taken from H2O to Replace Electrons Lost from P680
1. E- transportation：Mn complex → D → P680 →P680* → Chl a → Pheo → QAQB → PQ
2. Electrons flow from Pheo via specialized molecules of plastoquinone to a pool of plastoquinone (PQ)
within the membrane
3. Plastoquinone is mobile within the membrane (lipid nature) and hence serves to shuttle electrons
from the PSII supramolecular complex to the cytochrome b6 f complex
4. plastoquinone is an analog of coenzyme Q
 Electrons from PSII Are Transferred to PSI via the Cytochrome b6 f Complex
1. The cytochrome b6 f or plastoquinol:plastocyanin oxidoreductase
2. This complex is structurally and functionally homologous to the cytochrome bc1 complex (Complex
III) of mitochondria
3. includes the 2 heme-containing electron transfer proteins、Fe-S clusters, which also participate in
electron transport
4. The purpose of this complex is to mediate the transfer of electrons from PSII to PSI and to pump
protons across the thylakoid membrane via a plastoquinone-mediated Q cycle
5. Using the energy of an oxidation-reduction reaction to create a proton gradient across a membrane
6. This cyclic flow yields no O2 evolution or NADP+ reduction but can lead to ATP synthesis via so-called
cyclic photophosphorylation
 Plastocyanin Transfers Electrons from the Cytochrome b6 f Complex to PSI
1. Plastocyanin (PC) is an electron carrier along the inside of the thylakoid, aptly suited to its role in
shuttling electrons between the cytochrome b6f complex and PSI
2. the role of plastocyanin is directly analogous to the role of mitochondrial cytochrome c
3. PSI is a light-driven plastocyanin : ferredoxin oxidoreductase
4. Electron transportation：cytochrome c → PC → P700 → P700* → ferredoxin → Fd → Fp
5. Ferredoxin : NADP+ reductase this Fd series ends with a soluble form of ferredoxin, Fds, which serves
as the immediate electron donor to the flavoprotein (Fp) that catalyzes NADP1 reduction
 Summary
1. 高等植物進行光反應的過程中，天線色素吸收光能後將能量傳遞給光系統(PSI、PSII)的反應
中心 P700 或 P680 的葉綠素 a 分子，葉綠素 a 分子吸收能量後會轉變為高能量的激動態
(excited state)，以致其分子上的電子被擊發出來
2. 被擊發出來的高能電子會被囊狀膜上的電子傳遞鏈蛋白接收；其中電子不再重覆使用的稱為
非循環式電子傳遞鏈，其過程為 PSII 吸收光能後，促進水的光解(2H2O→O2＋4H+＋4e－)釋
放電子，此電子經由 PSII 轉送給 PSI，再由 PSI 傳遞給 NADP+而形成 NADPH＋H+。而 NADPH
＋H+中的電子最後則作為二氧化碳轉換為碳水化合物的還原劑。電子由 PSII 轉送給 PSI 的過
程 中 ， 因 傳 遞 蛋 白 對 電 子 的 親 和 力 不 同 ， 電 子 會 先 後 傳 給 ： pheophytin(pheo) →
plastoquinone(PQ)→cytochrome f(Cyt f)→plastocyanin(PC)，在 PQ 與 Cytf 間可以產生質子濃度
梯度，使質子在囊狀膜中累積高濃度，高濃度質子通過膜上質子通道由囊中往外運送時，經
酵素 ATPase 的催化作用而產生能量 ATP
21-4 What Is the Molecular Architecture of Photosynthetic Reaction Centers?
 The R. viridis Photosynthetic Reaction Center Is an Integral Membrane Protein
1. R. viridis is a photosynthetic prokaryote with a single photosystem that resembles PSII (composed
of L、M、H、cytochrome)
 2. The cytochrome subunit contains four heme groups; the N-terminal amino acid of this protein is Cys

 Photosynthetic Electron Transfer by the R. viridis Reaction Center Leads to ATP Synthesis
1. R. viridis reaction center is coupled to cyt b/c1 complex through quinone pool (Q)
2. Photo-excitation of the R. viridis RC leads to reduction of a quinone, Q, to form QH2. Oxidation of
QH2 by the cytochrome bc1 complex leads to H+ translocation for ATP synthesis
3. The use of light energy to drive ATP synthesis by the concerted action of these membrane proteins
is called photophosphorylation
 The Molecular Architecture of PSII Resembles the R. viridis Reaction Center Architecture
1. T. elongatus PSII is a homodimeric structure, each monomer having 23 different protein substances
and 34 transmembrane 𝛼-helical
2. D1 and D2 subunits of PSII (core) are similar to L and M subunits of R. viridis reaction center
3. Electron transfer from QA to QB by Fe is similar to electron transfer in R. viridis
4. Each plastoquinone that enters the QB site accepts two electrons derived from water and two H+
from the stroma before it is released into the membrane as the hydroquinone PQH2

 The Molecular Architecture of PSI Resembles the R. viridis Reaction Center and PSII Architecture
1. All of the electron-transferring prosthetic groups essential to PSI function are localized to just three
polypeptides: PsaA, PsaB, and PsaC (they provide a docking site for ferredoxin)
2. PsaA and PsaB compose the reaction center heterodimer (integral membrane complex)
3. PsaC interacts with the stromal face of the PsaA–PsaB heterodimer of thylakoid membrane (carries
two Fe-S clusters)
 4. PSI consists of three pairs of chlorophyll molecules: P700 (located at luminal side of dimer) and two
additional Chl a pairs
 How Do Green Plants Carry Out Photosynthesis?
1.
the structure of a plant membrane protein supercomplex consisting of the PSI reaction center and
its lightharvesting antenna LHC1 (light-harvesting complex 1
2. Many Chl molecules and other light-harvesting molecules of supercomplex form an integrated
network for highly efficient transfer of light energy into P700
21-5 What Is the Quantum Yield of Photosynthesis?
1. The quantum yield of photosynthesis is defined as the amount of product formed per equivalent of
light input (the amount of O2 evolved per photon)
2. 7 H+ contributed to the proton gradient across the thylakoid membrane for each pair of electrons
moving from H2O to NADP+
 2 into the lumen upon oxidation of a water molecule
 4 into the lumen from oxidation of PQH2 by the cytochrome b6 f complex
 1 H+ disappearing from the stroma as NADP+ is reduced to NADPH
3. 4 hv per photosystem (8 quanta) total would drive the evolution of 1 O2, the reduction of 2 NADP+,
and a contribution of 14 H+ to the proton gradient
4. The H+/ATP ratio depends on the number of c-subunits in the F1F0-ATP synthase possessed by a cell
or organism → 3 ATP are formed per 14 H+
5. 2 moles of NADPH, 3 moles of ATP, and 1 mole of O2
21-6 How Does Light Drive the Synthesis of ATP?

 Overview
1. The conversion of light energy to chemical energy results in electron-transfer reactions, which lead
to the generation of reducing power
2. Coupled with these electron transfers, protons are driven across the thylakoid membranes from the
stromal side to the lumenal side
 3. protons are produced in the thylakoid lumen upon photolysis of water by PSII
4. The oxidation–reduction events as electrons pass through the plastoquinone pool and the Q cycle
are another source of proton translocations
5. The proton transfer accompanying NADP+ reduction also can be envisioned as protons being taken
from the stromal side of the thylakoid vesicle
 The Mechanism of Photophosphorylation Is Chemiosmotic
1. It also shares the property of being a barrier to the passive diffusion of H+ ions
2. Photosynthetic electron transport thus establishes an electrochemical gradient, across the thylakoid
membrane with the lumen, side accumulating H+ ions relative to the stroma of the chloroplast

 Cyclic Photophosphorylation Generates ATP but Not NADPH or O2

1. In cyclic photophosphorylation, the electron hole in P700+ created by electron loss from P700 is
filled not by an electron derived from H2O via PSII but by a cyclic pathway in which the photoexcited
electron returns ultimately to P700+
2. The activated e- lost from PSI back through PQ, the cytochrome b6 f complex, and plastocyanin to
re-reduce P700+
3. In cyclic photophosphorylation, ATP is the product of energy conversion. No NADPH is generated,
and because PSII is not involved, no oxygen is evolved
4. cyclic photophosphorylation provides a mechanism for supplementing ATP production
 Photophosphorylation Can Occur in Either a Noncyclic or a Cyclic Mode

21-7 How Is Carbon Dioxide Used to Make Organic Molecules?

 Ribulose-1,5-Bisphosphate Is the CO2 Acceptor in CO2 Fixation
1. A unique ability of plants and algae
2. Calvin found that Chlorella (綠藻) could take up 14CO2 and produce 3-phosphoglycerate (3C)
3. What was actually happening was that CO2 was combining with a 5C sugar to form 6C intermediate
 than breaks down to 2 3PG
4. The five-carbon CO2 acceptor was identified as ribulose-1,5-bisphosphate (RuBP), and the enzyme
catalyzing this key reaction of CO2 fixation is ribulose bisphosphate carboxylase/oxygenase (Rubisco)
5. Rubisco is found in the chloroplast stroma (the world’s most abundant protein)
6. Rubisco 3 forms E inactive, EC inactive(carbamylated), ECM active (when CO2 added to Lys and with
Mg2+ bound)
7. RuBP (substrate) is inhibitor and must be released from inactive rubisco by rubisco activase
8. Mg2+ at the active site aids in stabilizing the 2,3-enediol transition state (I) for CO2 addition and in
facilitating the carbon–carbon bond cleavage that leads to product formation

 2-Carboxy-3-Keto-Arabinitol Is an Intermediate in the Ribulose-1,5-Bisphosphate Carboxylase Reaction

1. The addition of CO2 to ribulose-1,5-bisphosphate results in the formation of an enzyme-bound
intermediate, 2-carboxy-3-keto-arabinitol (II)
2. CO2, not HCO3-, is a true substrate
 CO2 Fixation into Carbohydrate Proceeds via the Calvin–Benson Cycle
1. The set of reactions that transforms 3-phosphoglycerate into hexose is named the Calvin cycle
2. not only must carbohydrate appear as an end product, but the 5-C acceptor, RuBP, must be
regenerated to provide for continual CO2 fixation
3. 6(1), or 6 CO2, condense with 6(5) or 6 RuBP to give 12 3-phosphoglycerates
4. 12(3)s are then rearranged in the Calvin cycle to form one hexose, 1(6), and regenerate the six 5-
carbon (RuBP) acceptors
 The Enzymes of the Calvin Cycle Serve Three Metabolic Purposes
1. Most of the enzymes mediating the reactions of the Calvin cycle also participate in either glycolysis
or the pentose phosphate pathway
2. the NADPH and ATP produced in the light reactions are consumed
3. reactions starts with ribulose bisphosphate carboxylase catalyzing formation of 3-phosphoglycerate
from CO2 and RuBP and concludes with phosphoribulose kinase, which forms RuBP
4. total of 18 equivalents of ATP consumed in hexose formation are expended：12 to form 1,3-BPG
and 6 to form RuBP
5. All 12 NADPH equivalents are used in reaction 3 (NADPH-specific G-3-P dehydrogenase)

 The Carbon Dioxide Fixation Pathway Is Indirectly Activated by Light

1. when light energy is available to generate ATP and NADPH for CO2 fixation, the Calvin cycle proceeds.
In the dark, when ATP and NADPH cannot be produced by photosynthesis, fixation of CO2 ceases
2. Light regulation of CO2 fixation prevents a substrate cycle between cellular respiration and hexose
synthesis by CO2 fixation
 3. Actives of Calvin cycle enzymes in stroma are coordinated with photosynthesis
 Light Induces pH Changes in Chloroplast Compartments (Because rubisco and rubisco activase
are more active at pH 8, CO2 fixation is activated as stromal pH rises)
 Light Energy Generates Reducing Power (reduced ferredoxin and NADPH)
 Light Induces Movement of Mg2+ Ions from the Thylakoid Vesicles into the Stroma
A. This efflux of Mg2+ somewhat counteracts the charge accumulation due to H+ influx and is
one reason why the membrane potential change in response to proton pumping is less in
chloroplasts than in mitochondria
B. Both ribulose bisphosphate carboxylase and F-1,6-BP are Mg2+-activated enzymes, and Mg2+
flux into the stroma as a result of light-driven proton pumping stimulates the CO2 fixation
pathway at these key steps
4. 光也會影響暗反應的酵素活性(indirectly)

21-8 How Does Photorespiration Limit CO2 Fixation?

 Photorespiration
1. Light-driven uptake of O2 and release of CO2 is termed photorespiration
2. RuBP oxygenase reaction diminishes plant reproductivity because it leads to loss of RuBP, the
essential CO2 acceptor
3. The ratio of carboxylase to oxygenase activity in vivio about 3 or 4 to 1
 Tropical Grasses Use the Hatch–Slack Pathway to Capture Carbon Dioxide for CO2 Fixation
1. Ribulose biphosphate + O2 with ribulose biphosphate carboxylase → wasteful cleavage of RuBP
2. The C-4 pathway is not an alternative to the Calvin cycle series of reactions or even a net CO2 fixation
scheme (Hatch–Slack pathway)
3. The C-4 compounds serving as CO2 transporters are malate or aspartate
4. Compartmentation of these reactions to prevent photorespiration involves the interaction of two
cell types: mesophyll cells (葉肉細胞)and bundle sheath cells (維管束鞘細胞)
5. mesophyll cells take up CO2 at the leaf surface, where O2 is abundant, and use it to carboxylate PEP
to yield OAA in a reaction catalyzed by PEP carboxylase
6. This 4C dicarboxylic acid is then either reduced to malate by an NADPH-specific malate
dehydrogenase or transaminated to give aspartate in the mesophyll cells
7. The 4-C CO2 carrier (malate or aspartate) is then transported to the bundle sheath cells, where it is
decarboxylated to yield CO2 and a 3-C product
8. The CO2 is fixed into organic carbon by the Calvin cycle localized (bundle sheath cells), and the 3C
product is returned to the mesophyll cells, where it is reconverted to PEP in preparation to accept
another CO2 (Pi kinase reinitiates the cycle)