5 - Electron Donors and Electron Acceptors - Handout

4.
Electron Donors and Electron Acceptors
◼ oxidation-reduction (Redox) reactions

◼ reduction potential
◼ a redox couple
◼ redox tower
◼ redox intermediary
◼ redox reactions in cells
◼ example of redox reactions in
environmental biotechnology
1
Conceptual model of the subsurface contaminant plume's
microbial geochemistry.
(Nonaqueous phase liquid)
The model shows the right to left progression of what electron

acceptors are being used by subsurface microbial communities to
degraded dissolved oil constituents in groundwater. U.S. Geological Survey
Living Wires of the Ocean Floor
by Gemma Reguera
http://schaechter.asmblog.org/schaechter/2013/01/living-wires-of-
the-ocean-floor.html
nitrate (NO3-)
manganese (Mn[IV])
Fe[III]
sulfate (SO4-2)
CO2
3
異化代謝
• In a cell, energy released from catabolic reactions is used to
synthesize energy rich compound, such as ATP
• Reactions that release sufficient energy to form ATP 異化代謝 (產生能量) :

例如透過細胞呼吸，分
→ oxidation-reduction type (abbreviation: redox) 解有機物質以獲取能量
• Oxidation/Reduction
oxidation: removal of an e-; reduction: addition of an e-
• electron cannot exist alone in solution

→ Redox reactions occur in pairs (two half reactions)
Electron donor: the substance oxidized in a redox reaction
Electron acceptor: the substance reduced in a redox reaction
Redox reaction
Half reaction
electron donor electron acceptor
donating e–
Formation Net reaction

Half reaction of water
accepting e–
Figure 3.8
Reduction potential
• Reduction potential 還原電位差 (競爭/得到/搶 e-的能力)
• substances differ in their tendency to donate electrons or accept
electrons.
• expressed as their Reduction potential (E0)
• E0′ → standard condition, pH = 7 標準還原電位差
• measure in volts (V)
• half reactions written as reductions
e.g. 2H+/H2 -0.42V

½ O2/H2O +0.82V
in writing a redox couple,
left → the oxidized form of the couple
right → the reduced form of the couple
Reduction potential
• Substances can be either electron donors or electron acceptors under
different circumstances (redox couple)
e.g. 2H+/H2 -0.42V

Fe+3/Fe+2 +0.20V
½ O2/H2O +0.82V
• In reaction between two redox couple,

a redox couple with a more negative E0′ → donates electrons
a redox couple with a more positive E0′ → receives electrons
2H+/H2 -0.42V → strong tendency to release e-
½ O2/H2O +0.82V → strong tendency to receive e-
Redox tower
• The redox tower represents the range of possible reduction
potentials in nature (Figure 3.9)
• The most negative redox couple at the top of the tower
• The most positive redox couple at the bottom of the tower
• reduced substance at the top of the tower
→ greatest tendency to donate e-
• oxidized substance at the bottom of the tower
→ greatest tendency to accept e-
• The farther the electrons "drop" (ΔE0′), the greater the amount of
energy released
→ ΔE0′ is proportional to ΔG0′
Figure 3.9
ΔE0′ is proportional to ΔG0′
Standard Free Energy 標準自由能變化
ΔG0′ = - nF ΔE0′
ΔG0′ = Gibbs free energy
n = number of e- transferred
F = Faraday constant 96.485 kJ /( V · mol)
ΔE0′ = E0′(oxidizing agent) - E0′(reducing agent)
ΔG<0: reaction is spontaneous in the direction

written (i.e., the reaction is exergonic) 放能反應
ΔG>0: reaction is not spontaneous and the
process proceeds spontaneously in the reserve
direction. To drive such a reaction, we need to
have input of free energy (i.e., the reaction is
endergonic) 吸收/需要能量的
Figure 3.9
延胡索酸二甲酯琥珀酸鹽
ΔG0′ = - nF ΔE0′
計算:
Conceptual model of the subsurface contaminant plume's
microbial geochemistry.
The model shows the right to left progression of what electron

acceptors are being used by subsurface microbial communities to
degraded dissolved oil constituents in groundwater. U.S. Geological Survey
Fig. 4.15.
hydrogen sulfide (H2S)

sulfate (SO4-2)
methane (CH4)
oxygen (O2)
nitrate (NO3-)
?
13
• Redox reactions in cells are mediated by small molecules
中間物；媒介物
• A very common redox intermediary (carriers) is the coenzyme –
adenine dinucleotide (NAD+) 菸鹼醯胺腺嘌呤二核苷酸
NAD+/NADH -0.32V (2e- and 2H+)
NADH → strong e- donor
透過輔酶如NAD+/NADH可使化學上不同的
NAD+ → weak e- acceptor 電子提供者和電子接受者可以作用，增加細
胞中可發生氧化還原反應的多樣性
• coenzymes such as NAD+/NADH increase the diversity of redox

reactions possible in a cell by allowing chemically dissimilar
electron donor and acceptors to interact, with the coenzyme act as
the intermediary (Figure 3.10)
• NAD+ and NADH facilitate redox reactions without being
consumed; they are recycled (Figure 3.11)
• NADP+/NADPH → anabolic (biosynthetic) reaction
Other redox carriers
• Nicotinamide adenine dinucleotide (NAD+/NADH)
a co-enzyme
carriers 2 electrons (e-) and 2 protons (H+)
• nicotinamide adenine dinucleotide phosphate (NADP+/ NADPH)
accepts 2 electrons and 1 proton.
• Flavin adenine dinucleotide (FAD/FADH) and
flavin mononucleotide (FMN/FMNH)
carry 2 electrons and 2 protons each
• Coenzyme Q (CoQ)/ubiquinone
carries 2 electrons and 2 protons.
• Cytochromes
carry 1 electron at a time
• Iron-sulfur (Fe-S) proteins, such as ferredoxin
carry 1 electron at a time
菸鹼醯胺腺嘌呤二核苷酸
NAD+ NADH + H+
Nicotinamide
NAD+/ NADH
Adenine E0′ = –0.32 V
In NADP+, this OH has a

phosphate attached.
Figure 3.10
Enzyme I reacts with e–
NAD+ reduction donor and oxidized form
NAD+
Active of coenzyme, NAD+. Enzyme–substrate complex
binding site
1.
NADH and reaction
site
product are formed.
Enzyme I
2.
Substrate
+
NAD+ + (e– donor)
NADH
NADH binding +
site Product
4.
Product Active
site
Enzyme Il Substrate
3. (e– acceptor)
NAD+ is Enzyme–substrate
released. complex
Enzyme II reacts with e–
NADH oxidation acceptor and reduced
form of coenzyme, NADH.
Figure 3.11
The electron transport chain
he electron tower concept is useful to illustrate energy yielding redox reactions in biology. Theoretically, any reaction at
the bottom of the electron tower can be coupled to a reaction at the top. The amount of energy (ΔG) available from a
given reaction is proportional to the difference in the reduction potential of the redox couples in question (Adapted from
Hinks et al., 2017).
https://www.researchgate.net/figure/The-electron-tower-concept-is-useful-to-illustrate-energy-yielding-redox-
reactions-in_fig1_343932608

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4.

Electron Donors and Electron Acceptors

◼ oxidation-reduction (Redox) reactions

(Nonaqueous phase liquid)

The model shows the right to left progression of what electron

• Reactions that release sufficient energy to form ATP 異化代謝 (產生能量) :

• electron cannot exist alone in solution

Formation Net reaction

e.g. 2H+/H2 -0.42V

e.g. 2H+/H2 -0.42V

• In reaction between two redox couple,

F = Faraday constant 96.485 kJ /( V · mol)

ΔE0′ = E0′(oxidizing agent) - E0′(reducing agent)

ΔG<0: reaction is spontaneous in the direction

The model shows the right to left progression of what electron

hydrogen sulfide (H2S)

• coenzymes such as NAD+/NADH increase the diversity of redox

In NADP+, this OH has a

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