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10.12 Phototrophy 211

supplied with reduced organic carbon sources such as glucose Chlorophyll-based phototrophy
or amino acids.
Light

1. How do chemolithotrophs obtain their ATP and e-

NADH? What is their most common source of carbon?
Chlorophyll
e- Electron transport chain e-
2. Describe energy production by hydrogen-oxidizing or NAD(P)+
bacteriochlorophyll
bacteria, nitrifying bacteria, and sulfur-oxidizing NAD(P)H
bacteria.
photo phos
3. Why can hydrogen-oxidizing bacteria and archaea ATP
PMF
donate electrons to NAD while sulfur- and ammonia-
oxidizing bacteria and archaea cannot? Carbon source
(often CO2) Biosynthesis
4. What is reverse electron flow and why do many
chemolithotrophs perform it?
Rhodopsin-based phototrophy
5. Arsenate is a compound that inhibits substrate-level
phosphorylation. Compare the effect of this compound Light
on an H2-oxidizing chemolithotroph, on a sulfite-
oxidizing chemolithotroph, and on a chemoorgano-
troph carrying out fermentation. Bacteriorhodopsin photo phos
(archaeorhodopsin) PMF ATP
or proteorhodopsin

Carbon source Biosynthesis

10.12 PHOTOTROPHY
Many microorganisms derive energy from the oxidation of inor- Figure 10.26 Phototrophic Fueling Reactions. Phototrophs
ganic and organic compounds, but many others capture the energy use light to generate a proton motive force (PMF), which is then used to synthe-
size ATP by a process called photophosphorylation (photo phos). The process
in light and use it to synthesize ATP and reducing power (e.g.,
requires light-absorbing pigments. When the pigments are chlorophyll or bac-
NADPH) (figure 10.1). When the ATP and reducing power are teriochlorophyll, the absorption of light triggers electron flow through an electron
used to reduce and incorporate CO2 (CO2 fixation), the process is transport chain, accompanied by the pumping of protons across a membrane.
called photosynthesis. Photosynthesis is one of the most signifi- The electron flow can be either cyclic (dashed line) or noncyclic (solid line),
cant metabolic processes on Earth because almost all our energy depending on the organism and its needs. Rhodopsin-based phototrophy dif-
fers in that the PMF is formed directly by the light-absorbing pigment, which is
is ultimately derived from solar energy. Photosynthetic organ-
a light-driven proton pump. Many phototrophs are autotrophs and must use
isms serve as the base of most food chains in the biosphere. One much of the ATP and reducing power they make to fix CO2.
type of photosynthesis is also responsible for replenishing our
supply of O2. Although most people associate photosynthesis
with plants, over half the photosynthesis on Earth is carried out and reducing power. These are then used to fix CO2 and synthe-
by microorganisms (table 10.5). size cell constituents in the dark reactions. In this section, three
Photosynthesis is divided into two parts. In the light reac- types of phototrophy are discussed: oxygenic photosynthesis,
tions, light energy is trapped and converted to chemical energy anoxygenic photosynthesis, and rhodopsin-based phototrophy
(figure 10.26). The dark reactions of photosynthesis are reviewed
in chapter 11. >> CO2 fixation (section 11.3)

Table 10.5 Diversity of Phototrophic

Organisms Light Reactions in Oxygenic
Eucaryotic Organisms Procaryotic Organisms Photosynthesis
Phototrophic eucaryotes and cyanobacteria carry out oxygenic
Plants Cyanobacteria
photosynthesis, so named because oxygen is generated and
Multicellular green, brown, Green sulfur bacteria released into the environment when light energy is converted to
and red algae Green nonsulfur bacteria chemical energy. Central to this process, and to all other photo-
trophic processes, are light-absorbing pigments (table 10.6). In
Unicellular protists Halobacterium (archaeon)
(e.g., euglenoids, Purple sulfur bacteria oxygenic phototrophs, the most important pigments are the chlo-
dinoflagellates, diatoms) Purple nonsulfur bacteria rophylls. Chlorophylls are large planar molecules composed of
four substituted pyrrole rings with a magnesium atom coordinated
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212 Chapter 10 Catabolism: Energy Release and Conservation

Table 10.6 Properties of Chlorophyll-Based Photosynthetic Systems

Green Bacteria, Purple

Property Eucaryotes Cyanobacteria Bacteria, and Heliobacteria

Photosynthetic pigment Chlorophyll a Chlorophyll a Bacteriochlorophyll

Number of photosystems 2 2 1
Photosynthetic electron donors H2O H2O H2, H2S, S, organic matter
O2 production pattern Oxygenic Oxygenica Anoxygenic
Primary products of energy conversion ATP ⫹ NADPH ATP ⫹ NADPH ATP

Carbon source CO2 CO2 Organic or CO2

a
Some cyanobacteria can function anoxygenically under certain conditions. For example, Oscillatoria can use H2S as an electron donor instead of H2O.

Bacteriochlorophyll a (the second absorption peak for chlorophyll a is at 430 nm).

CH3 Because chlorophylls absorb primarily in the red and blue ranges,
C O green light is transmitted, and these organisms appear green. A
long hydrophobic tail attached to the chlorophyll ring aids in its
attachment to membranes, the site of the light reactions.
H O
H CH2 C Other photosynthetic pigments also trap light energy. The most
C H
CH3 Chlorophyll b widespread of these are the carotenoids, long molecules, usually
C C CH3
yellowish in color, that possess an extensive conjugated double
C
C C
C C 2H 5
bond system (figure 10.28). β-Carotene is present in cyanobacte-
H3 C C I II C H
H ria belonging to the genus Prochloron and most photosynthetic
N N
C C C C 2H 5 protists; fucoxanthin is found in protists such as diatoms and dino-
Pyrrole H C Mg C H flagellates. Red algae and cyanobacteria have photosynthetic
rings
C C Bacteriochlorophyll a pigments called phycobiliproteins, consisting of a protein with a
N N
H linear tetrapyrrole attached (figure 10.28). Phycoerythrin is a red
C IV III
H3C C C C CH3 pigment with a maximum absorption around 550 nm, and phyco-
C C C Chlorophyll a cyanin is blue (maximum absorption at 620 to 640 nm).
HH
H Carotenoids and phycobiliproteins are often called accessory
C C C C
H H
H
pigments because of their role in photosynthesis. They are
O C O
O C important because they absorb light in the range not absorbed
O
O CH3
by chlorophylls (the blue-green through yellow range; about
470–630 nm) (see figure 19.4). This light is transferred to chloro-
R phyll. In this way accessory pigments make photosynthesis more
Figure 10.27 Chlorophyll Structure. The structures of chloro- efficient over a broader range of wavelengths. In addition, this
phyll a, chlorophyll b, and bacteriochlorophyll a. The complete structure of allows organisms to use light not used by other phototrophs in
chlorophyll a is given. Only one group is altered to produce chlorophyll b, their habitat. Accessory pigments also protect microorganisms
and two modifications in the ring system are required to change chlorophyll from intense sunlight, which could oxidize and damage the pho-
a to bacteriochlorophyll a. The side chain (R) of bacteriochlorophyll a may be
tosynthetic apparatus.
either phytyl (a 20-carbon chain also found in chlorophylls a and b) or gera-
nylgeranyl (a 20-carbon side chain similar to phytyl but with three more Chlorophylls and accessory pigments are assembled in highly
double bonds). organized arrays called antennas, whose purpose is to create a
large surface area to trap as many photons as possible. An antenna
has about 300 chlorophyll molecules. Light energy is captured in
to the four central nitrogen atoms (figure 10.27). Several chloro- an antenna and transferred from chlorophyll to chlorophyll until
phylls are found in eucaryotes; the two most important are it reaches a reaction-center chlorophyll pair that is directly
chlorophyll a and chlorophyll b. These two molecules differ involved in photosynthetic electron transport. In oxygenic photo-
slightly in their structure and spectral properties. When dissolved trophs, there are two kinds of antennas associated with two
in acetone, chlorophyll a has a light absorption peak at 665 nm; different photosystems (figure 10.29). Photosystem I absorbs
the corresponding peak for chlorophyll b is at 645 nm. In addition longer wavelength light (ⱖ680 nm) and funnels the energy to a
to absorbing red light, chlorophylls also absorb blue light strongly reaction center chlorophyll a pair called P700. The term P700
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10.12 Phototrophy 213

H3C
CH3 CH3 CH3 H3C

CH3 CH3 CH3 CH3

CH3
β-Carotene (a carotenoid)

O O
HO HO
OCOCH 3
Fucoxanthin (a carotenoid)

COOH COOH
CH3 CH2 CH2 CH3
CH3 CH CH3 CH2 CH2 CH3 CH3 CH2

O O
N N N N
H H H
Phycocyanobilin

Figure 10.28 Representative Accessory Pigments. Beta-carotene is a carotenoid found in photosynthetic protists and plants. Note that it has a
long chain of alternating double and single bonds called conjugated double bonds. Fucoxanthin is a carotenoid accessory pigment in several divisions of algae (the
dot in the structure represents a carbon atom). Phycocyanobilin is an example of a linear tetrapyrrole that is attached to a protein to form a phycobiliprotein.

signifies that this molecule most effectively absorbs light at a photosystem II antenna absorbs light energy and excites P680,
wavelength of 700 nm. Photosystem II traps light at shorter which then reduces pheophytin a. Pheophytin a is chlorophyll a
wavelengths (680 nm) and transfers its energy to the reaction in which two hydrogen atoms have replaced the central magne-
center chlorophyll pair P680. sium. Electrons subsequently travel to the plastoquinone pool
When the photosystem I antenna transfers light energy to and down an ETC to reduce P700. Now P680 must also be
P700, P700 absorbs the energy and is excited, and its reduction reduced if it is to accept more light energy. Figure 10.29 indicates
potential becomes very negative. This allows P700 to donate its that the standard reduction potential of P680 is more positive
excited, high-energy electron to a specific acceptor, probably a than that of the 1/2O2/H2O redox couple. Thus H2O can be used
special chlorophyll a molecule or an iron-sulfur protein. The to donate electrons to P680 resulting in the release of oxygen.
electron is eventually transferred to ferredoxin and then travels in Because electrons flow from water to NADP with the aid
either of two directions. In the cyclic pathway (the dashed lines of energy from two photosystems, ATP is synthesized by non-
in figure 10.29), the electron moves in a cyclic route through a cyclic photophosphorylation. It appears that one ATP and one
series of electron carriers and back to the oxidized P700. The NADPH are formed when two electrons travel through the non-
pathway is termed cyclic because the electron from P700 returns cyclic pathway.
to P700 after traveling through the photosynthetic ETC. PMF is It is worth reemphasizing that although light is the source
formed during cyclic electron transport and used to synthesize of energy for chlorophyll-based phototrophy, the process used
ATP. This process is called cyclic photophosphorylation because to make ATP is virtually the same as seen for chemotrophs:
electrons travel in a circle and ATP is formed. Only photosystem oxidation-reduction reactions occurring in ETCs generate a
I participates. PMF that is used by ATP synthase to make ATP. Furthermore,
Electrons also can travel in a noncyclic pathway involving just as is true of mitochondrial electron transport, photosynthetic
both photosystems. P700 is excited and donates electrons to fer- electron transport takes place within a membrane. Chloroplast
redoxin as before. In the noncyclic route, however, reduced granal membranes contain both photosystems and their antennas.
ferredoxin reduces NADP to NADPH (figure 10.29). Because Figure 10.30 shows a thylakoid membrane carrying out noncy-
the electrons contributed to NADP cannot be used to reduce clic photophosphorylation by the chemiosmotic mechanism.
oxidized P700, photosystem II participation is required. It donates Protons move to the thylakoid interior during photosynthetic
electrons to oxidized P700 and generates ATP in the process. The electron transport and return to the stroma when ATP is formed.
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214 Chapter 10 Catabolism: Energy Release and Conservation

–1.4
P*700
Reaction center
–1.2

–1.0
A or FeS

– 0.8 P*680 FeS

– 0.6
Fd
Redox potential (volts)

Pheo. a Pyridine nucleotide

) reductase (FAD)
– 0.4 clic
(Cy
NADP+
– 0.2
Cyt b 563 PS I NADPH + H+
Q 2e-
0.0
ADP + Pi 2 photons
PQ ATP
+ 0.2 Cyt b6
FeS
PS II Cyt f PC 2e-
+ 0.4 Antenna
2e- P700
(Noncyclic) 2 photons
+ 0.6
OEC
+ 0.8 Mn 2+(
H2O 2e - 3+)
Z 2e -
+ 1.0
1/
2H+ P680
2O2 +

Figure 10.29 Green Plant Photosynthesis. Electron flow during photosynthesis in higher plants. Cyanobacteria and eucaryotic algae are similar
in having two photosystems, although they may differ in some details. The carriers involved in electron transport are ferredoxin (Fd) and other FeS proteins;
cytochromes b6, b563, and f; plastoquinone (PQ); copper containing plastocyanin (PC); pheophytin a (Pheo. a); possibly chlorophyll a (A); and the unknown
quinone Q, which is probably a plastoquinone. Both photosystem I (PS I) and photosystem II (PS II) are involved in noncyclic photophosphorylation; only PS I
participates in cyclic photophosphorylation. The oxygen evolving complex (OEC) that extracts electrons from water contains manganese ions and the sub-
stance Z, which transfers electrons to the PS II reaction center.

It is believed that stromal lamellae possess only photosystem I 10 to 12 quanta of light energy are needed to reduce and incorpo-
and are involved in cyclic photophosphorylation alone. In cyano- rate one molecule of CO2 during photosynthesis.
bacteria, photosynthetic light reactions are located in thylakoid
membranes within the cell.
The dark reactions of oxygenic phototrophs use three ATPs Light Reactions in Anoxygenic
and two NADPHs to reduce one CO2 to carbohydrate (CH2O).
Photosynthesis
CO2  3ATP  2NADPH  2H  H2O →
Certain bacteria carry out a second type of photosynthesis called
(CH2O)  3ADP  3Pi  2NADP
anoxygenic photosynthesis. This phototrophic process derives
The noncyclic system generates one NADPH and one ATP per its name from the fact that molecules other than water are used as
pair of electrons; therefore four electrons passing through the an electron source and therefore O2 is not produced. The process
system produce two NADPHs and two ATPs. A total of 8 quanta also differs in terms of the photosynthetic pigments used, the par-
of light energy (4 quanta for each photosystem) is needed to pro- ticipation of just one photosystem, and the mechanisms used to
pel the four electrons from water to NADP. Because the ratio of generate reducing power. Three groups of bacteria carry out
ATP to NADPH required for CO2 fixation is 3:2, at least one anoxygenic photosynthesis: phototrophic green bacteria, photo-
more ATP must be supplied. Cyclic photophosphorylation prob- trophic purple bacteria, and heliobacteria. The biology and
ably operates independently to generate the extra ATP. This ecology of these organisms are described in more detail in chap-
requires absorption of another 2 to 4 quanta. It follows that around ters 18, 19, and 20.
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10.12 Phototrophy 215

Chloroplast

ADP + Pi ATP

Thylakoid Stroma

Stroma
Pyridine
nucleotide
Photons Photons reductase F1 ATP
Cytochrome 2H+ synthase
bf complex 2NADP+ 2NADPH
8H+
e-
Fd FAD
QA e- FeS
QB Cyt b6
4PQH2
e-
Pheo
FeS A F0
4PQ
e- P680
Cyt f P700
e– e–
Mn PC -Cu+
OEC
8H+ PC -Cu2+ Photosystem I 3H+
Photosystem II
2H2O O2 + 4H+
Thylakoid lumen

Figure 10.30 The Mechanism of Photosynthesis. An illustration of the chloroplast thylakoid membrane showing photosynthetic ETC function
and noncyclic photophosphorylation. The chain is composed of three complexes: PS I, the cytochrome bf complex, and PS II. Two diffusible electron carriers
connect the three complexes. Plastoquinone (PQ) connects PS I with the cytochrome bf complex, and plastocyanin (PC) connects the cytochrome bf complex
with PS II. The light-driven electron flow pumps protons across the thylakoid membrane and generates a PMF, which can then be used to make ATP. Water is
the source of electrons and the oxygen-evolving complex (OEC) produces oxygen.

Anoxygenic phototrophs have photosynthetic pigments called P870 while generating sufficient PMF to drive ATP synthesis by
bacteriochlorophylls (figure 10.27). In some bacteria, these are ATP synthase. Note that although both green and purple bacteria
located in membranous vesicles called chlorosomes. The absorp- lack two photosystems, the purple bacteria have a photosynthetic
tion maxima of bacteriochlorophylls (Bchl) are at longer apparatus similar to photosystem II of oxygenic phototrophs,
wavelengths than those of chlorophylls. Bacteriochlorophylls a whereas the green sulfur bacteria have a system similar to
and b have maxima in ether at 775 and 790 nm, respectively. In photosystem I. >> Class Alphaproteobacteria: Purple nonsulfur
vivo maxima are about 830 to 890 nm (Bchl a) and 1,020 to 1,040 bacteria (section 20.1)
nm (Bchl b). This shift of absorption maxima into the infrared Anoxygenic photoautotrophs face a further problem because
region better adapts these bacteria to their ecological niches. they also require reducing power (NAD[P]H or reduced ferre-
>> Photosynthetic bacteria (section 19.3) doxin) for CO2 fixation and other biosynthetic processes. They
Many differences found in anoxygenic phototrophs are are able to generate reducing power in at least three ways,
because they have a single photosystem. Because of this, they depending on the bacterium. Some have hydrogenases that are
are restricted to cyclic photophosphorylation and are unable to used to produce NAD(P)H directly from the oxidation of hydro-
produce O2 from H2O. Indeed, almost all anoxygenic photo- gen gas. This is possible because hydrogen gas has a more
trophs are strict anaerobes. A tentative scheme for the negative reduction potential than NAD (see table 9.1). Others,
photosynthetic ETC of a purple nonsulfur bacterium is given in such as the photosynthetic purple bacteria, use reverse electron
figure 10.31. When the reaction-center bacteriochlorophyll flow to generate NAD(P)H (figure 10.31). In this mechanism,
P870 is excited, it donates an electron to bacteriopheophytin. electrons are drawn off the photosynthetic ETC and “pushed”
Electrons then flow to quinones and through an ETC back to to NAD(P) using PMF. Electrons from electron donors such as
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11.3 CO2 Fixation 223

crucial to life on Earth because it provides the organic matter on

CH2O P CARBOXYLATION
which heterotrophs depend. << Chemolithotrophy (section 10.11); PHASE
Phototrophy (section 10.12); >> Biogeochemical cycling: Carbon C O

cycle (section 25.1) HCOH Ribulose 1,5-

bisphosphate
Four different CO2-fixation pathways have been identified in HCOH
microorganisms. Most autotrophs use the Calvin cycle, which is CH2O P
also called the Calvin-Benson cycle or the reductive pentose Ribulose
CO2
phosphate cycle. The Calvin cycle is found in photosynthetic 1,5-bisphosphate H 2O

eucaryotes and most photosynthetic bacteria. It is absent in some carboxylase

obligatory anaerobic and microaerophilic bacteria. Autotrophic CH2O P COOH

archaea also use an alternative pathway for CO2 fixation. We con- HOCH + HCOH 3-phosphoglycerate
sider the Calvin cycle first and then briefly introduce the three COOH CH2O P
other CO2-fixation pathways.
Phosphoglycerate ATP
kinase
Calvin Cycle ADP
ADP
The Calvin cycle is also called the reductive pentose phosphate ATP O REDUCTION
cycle because it is essentially the reverse of the pentose phos- PHASE
C O P
phate pathway. Thus many of the reactions are similar, in
HCOH
particular the sugar transformations. The reactions of the Calvin 1,3-bisphosphoglycerate
cycle occur in the chloroplast stroma of eucaryotic autotrophs. CH2O P
NADPH + H+
In cyanobacteria, some nitrifying bacteria, and thiobacilli (sulfur-
Glyceraldehyde
oxidizing chemolithotrophs), the Calvin cycle is associated with 3-phosphate NADP+
inclusion bodies called carboxysomes. These polyhedral struc- dehydrogenase
Pi
tures contain the enzyme critical to the Calvin cycle and may be
the site of CO2 fixation. << Breakdown of glucose to pyruvate: H O
Pentose phosphate pathway (section 10.3) C
Glyceraldehyde CH2OH
The Calvin cycle is divided into three phases: carboxylation HCOH 3-phosphate
C O
phase, reduction phase, and regeneration phase (figure 11.5 and CH2O P
CH2O P
appendix II). During the carboxylation phase, the enzyme ribulose
DHAP
1,5-bisphosphate carboxylase, also called ribulose bisphosphate (1)
Ribulose 5-
carboxylase/oxygenase (Rubisco), catalyzes the addition of CO2 to REGENERATION Biosynthetic
phosphate
PHASE products
the five-carbon molecule ribulose 1,5-bisphosphate (RuBP), form- (5)
ing a six-carbon intermediate that rapidly and spontaneously splits
Fructose 1,6-bisphosphate
into two molecules of 3-phosphoglycerate (PGA). Note that PGA is Fructose 6-phosphate
an intermediate of the Embden-Meyerhof pathway (EMP), and Erythrose 4-phosphate
in the reduction phase, PGA is reduced to glyceraldehyde Ribose 5-phosphate
and other intermediates
3-phosphate by two reactions that are essentially the reverse of two
EMP reactions. The difference is that the Calvin cycle enzyme
glyceraldehyde 3-phosphate dehydrogenase uses NADP⫹ rather Figure 11.5 The Calvin Cycle. This overview of the cycle
than NAD⫹ (compare figures 11.5 and 10.5). Finally, in the regen- shows only the carboxylation and reduction phases in detail. Three ribu-
eration phase, RuBP is regenerated, so that the cycle can repeat. In lose 1,5-bisphosphates are carboxylated to give six 3-phosphoglycerates
in the carboxylation phase. These are converted to six glyceraldehyde 3-
addition, this phase produces carbohydrates such as glyceraldehyde
phosphates, which can be converted to dihydroxyacetone phosphate
3-phosphate, fructose 6-phosphate, and glucose 6-phosphate, all of (DHAP). Five of the six trioses (glyceraldehyde phosphate and dihydroxy-
which are precursor metabolites (figures 11.3 and 11.4). This por- acetone phosphate) are used to reform three ribulose 1,5-bisphosphates
tion of the cycle is similar to the pentose phosphate pathway and in the regeneration phase. The remaining triose is used in biosynthesis. The
involves the transketolase and transaldolase reactions. numbers in parentheses at the lower right indicate this carbon flow.
To synthesize fructose 6-phosphate or glucose 6-phosphate
6CO2 ⫹ 18ATP ⫹ 12NADPH ⫹ 12H⫹ ⫹ 12H2O →
from CO2, the cycle must operate six times to yield the desired
glucose ⫹ 18ADP ⫹ 18Pi ⫹ 12NADP⫹
hexose and reform the six RuBP molecules.
6RuBP ⫹ 6CO2 → 12PGA → 6RuBP ⫹ fructose-6-P Other CO2-Fixation Pathways
The incorporation of one CO2 into organic material requires three Certain bacteria and archaea fix CO2 using the reductive TCA
ATPs and two NADPHs. The formation of glucose from CO2 cycle, the 3-hydroxypropionate cycle, or the acetyl-CoA path-
may be summarized by the following equation. way. The reductive TCA cycle (figure 11.6) is used by some