12

The Importance of
Energy Changes and
Electron Transfer in
Metabolism

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12-1
12 Lesson Learning Outcomes
Upon completion of this lecture, students should
be able to:
• define proton and electron
• understand oxidation and reduction processes
• understand phosphorylation and
dephosphorylation
• identify function of adenosine triphosphate
(ATP)
• understand metabolism

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12-2
12 Nature of Metabolism
• Metabolism: the chemical reactions of
biomolecules
• catabolism:
catabolism: the breakdown of larger molecules into
smaller ones; an oxidative process that releases
energy
• anabolism
anabolism:: the synthesis of larger molecules from
smaller ones; a reductive process that requires energy
• oxidation
oxidation:: the loss of electrons; the substance that
loses the electrons is called a reducing agent
• reduction
reduction:: the gain of electrons; the substance that
gains the electrons is called an oxidizing agent

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12-3
12 Catabolism & Anabolism
Catabolism Anabolism
Polysac-
Fats charides Proteins
Catabolism Excretion
beakdown
of larger
molecules Fatty acids Monosac- Amino
Products of anabolism,
to smaller and glycerol charides Acids
including proteins and
ones nucleic acids
Small Anabolism energy and
molecules of proteins reducing
oxidation and the agents
release of energy Some nutrients and
Excretion Anabolism products of catabolism

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12-4
12 Redox Coenzymes
• Oxidation and reduction are most easily
recognized by writing balanced half-reactions
• conversion of ethanol to acetaldehyde is a two-
electron oxidation
O
CH3 CH2 OH CH3 CH + 2 H+ + 2 e -
Ethanol Acetaldehyde

• conversion of pyruvate to lactate is a two-electron

reduction
O OH
CH3 CCOO - + 2 H+ + 2 e - CH3 CHCOO-
Pyruvate Lactate
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12-5
12 NAD+/NADH
• Nicotinamide adenine dinucleotide (NAD+) is a
biological oxidizing agent
The plus sign on NAD+
represents the positive
charge on this nitrogen O Nicotinamide;
CNH 2 derived
O from niacin
-
O- P-O- CH 2 N+
O
O H H a β -N-glycosidic
H H bond
A MP
HO OH

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12-6
12 NAD+/NADH
Oxidation of ethanol by NAD +
NAD + + H+ + 2 e - NADH
O
CH3 CH2 OH CH3 CH + 2 H+ + 2 e -
O
CH3 CH2 OH + NAD + CH3 CH + NADH + H+
Ethanol Acetaldehyde

Reduction of pyruvate by NADH

NADH NAD + + H+ + 2 e -
O OH
CH3 CCOO - + 2 H+ + 2 e - CH3 CHCOO-
O OH
CH3 CCOO - + NADH + H+ CH3 CHCOO- + NAD +
Pyruvate Lactate
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12-7
12 FAD/FADH2
• Flavin adenine O
H3 C N H
dinucleotide N Flavin
(FAD) is also a H3 C

Riboflavin
N N O
biological CH2
oxidizing agent H C OH
H C OH Ribitol
H C OH
CH2
O
O= P-O- A MP
O-

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12-8
12 FAD/FADH2
O
H3 C N
NH
+ 2 H+ + 2 e -
H3 C N N O
Ad H O
FAD H3 C N
NH
H3 C N N O
Ad H
FAD H2

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12-9
12 FAD/FADH2
• FAD participates in several types of enzyme-
catalyzed oxidation/reduction reactions
• one is the oxidation of a C-C bond in a fatty acid
hydrocarbon chain to a C=C bond
Oxidation of the hydrocarbon chain:
- CH 2 - CH2 - - CH = CH - + 2 H+ + 2 e -

Reduction of FAD:
FAD + 2 H + + 2 e - FAD H2

- CH 2 - CH2 - + FAD FAD H2

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12-10
12 Coupled Reactions
• The coupling of energy-producing and energy-
requiring reactions is a central theme in the
metabolism of all organisms
• central to this process is ATP NH 2
N
N
O O O
- N
O- P - O- P - O- P - O- CH 2 N
O
O- O- O- H H
H H
HO OH

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12-11
12 Coupled Reactions
• phosphorylation of ADP to ATP requires energy
A DP + Pi + H+ A TP + H2 O ∆G °' = +30.5 kJ•mol -1

O O O O
- +
A MP- O-P- O - + O- P-OH + H A MP- O-P- O-P- O - + H2 O
-
O O- -
O -O
ADP ATP

• hydrolysis of ATP to ADP releases energy

A TP + H2 O A DP + Pi + H+ ∆G°' = -30.5 kJ•mol -1

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12-12
12 Anabolism & Catabolism
Figure 12.11 The role of ATP as an energy source

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12-13