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Oxidation
Energy-rich
molecule
Enzyme

Product

Reduction

+H+
H
H

H
H

2e
H+
H

NAD+

NAD+

NAD

NAD

NAD+
1. Enzymes that use NAD+
as a cofactor for oxidation
reactions bind NAD+ and the
substrate.

2. In an oxidationreduction
reaction, 2 electrons and
a proton are transferred
to NAD+, forming NADH.
A second proton is
donated to the solution.

3. NADH diffuses away


and can then donate
electrons to other
molecules.

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Electrons from food


2e

Energy released
for ATP synthesis
High energy

Low energy
1/ O
2 2

2H+

H2O
2

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Reduction

NH2 + 2H

O
NH2 + H+

C
Oxidation

N
O
O

CH2

N
O

O
OH

N
P
O

O
OH

N
O

H
OH

P
O

OH

NAD+: Oxidized form of nicotinamide

H
N

CH2

Adenine

NH2

OH

H
CH2

H
NH2

OH

CH2

Adenine
H

H
OH

OH

NADH: Reduced form of nicotinamide

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PEP
P

Enzyme

Enzyme
P
P

ADP

ATP

Adenosine

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Outer
mitochondrial
membrane

Glycolysis
Glucose
NADH

ATP

Intermembrane
space

Pyruvate

Pyruvate
Oxidation

NADH

Acetyl-CoA

Mitochondrial
matrix
CO2

CO2

NADH
Krebs
Cycle
FADH2
e
NAD+ FAD O2

ATP

H2O

e
Electron e
Transport Chain

Inner
mitochondrial
membrane

ATP

Chemiosmosis
ATP Synthase
H+

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Glycolysis

ATP

NADH
Pyruvate Oxidation

Krebs
Cycle

Electron Transport Chain


Chemiosmosis

Glycolysis begins
with the addition of
energy. Two highenergy phosphates
(P) from two
molecules of ATP
are added to the
6-carbon molecule
glucose, producing
a 6-carbon
molecule with two
phosphates.

Priming Reactions

6-carbon glucose
(Starting material)

ATP

ATP
ADP

ADP

Cleavage

6-carbon sugar diphosphate

3-carbon sugar
phosphate

3-carbon sugar
phosphate

Oxidation and ATP Formation

Pi

Pi

NAD+

NAD+

NADH

NADH

ADP

ADP

ATP

ATP

ADP

ADP

ATP

ATP

3-carbon
pyruvate

Then, the 6-carbon


molecule with two
phosphates is split in
two, forming two
3-carbon sugar
phosphates.

3-carbon
pyruvate

An additional
Inorganic phosphate
( Pi ) is incorporated
into each 3-carbon
sugar phosphate. An
oxidation reaction
converts the two
sugar phosphates
into intermediates
that can transfer a
phosphate to ADP to
form ATP. The
oxidation reactions
also yield NADH
giving a net energy
yield of 2 ATP and 2
NADH.

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CH2OH

Glycolysis: The Reactions


Glucose

Pyruvate Oxidation

Glucose
6-phosphate

ATP

Hexokinase
ADP

Krebs
Cycle

Glucose 6-phosphate
Phosphoglucose
isomerase

Fructose 6-phosphate
3

ATP

Phosphofructokinase
AD P
Fructose 1,6-bisphosphate
23. Rearrangement,
followed by a second
ATP phosphorylation.

CH2

O
O

CH2OH

CH2

CH2

NADH

NADH
Glyceraldehyde
3-phosphate
dehydrogenase
1,3-Bisphosphoglycerate
1,3-Bisphosphoglycerate
(BPG)
(BPG)
7

ADP

3-Phosphoglycerate
(3PG)

ATP

3-Phosphoglycerate
(3PG)

CH2OH

2-Phosphoglycerate
(2PG)

2-Phosphoglycerate
(2PG)
9

H 2O

H 2O

Enolase

Phosphoenolpyruvate
(PEP)

Phosphoenolpyruvate
(PEP)

ADP

10

ADP

ATP

Pyruvate kinase

ATP

Pyruvate

Pyruvate

CHOH
CH2

CH2

O
C

CHOH
P

CH2

8
Phosphoglyceromutase

H
C

CHOH

ADP

Phosphoglycerate
kinase

ATP

CH2

Glyceraldehyde
3-phosphate

NAD+

Pi

Dihydroxyacetone
Phosphate

Pi

1,3-Bisphosphoglycerate

Glyceraldehyde 3phosphate (G3P)


6

NAD+

89. Removal of water yields


two PEP molecules, each
with a high-energy
phosphate bond.
10. Removal of high-energy
phosphate by two ADP
molecules produces two
ATP molecules and two
pyruvate molecules.

3-Phosphoglycerate

7. Removal of high-energy
phosphate by two ADP
molecules produces two
ATP molecules and leaves
two 3PG molecules.

Dihydroxyacetone
phosphate

2-Phosphoglycerate

6. Oxidation followed by
phosphorylation produces
two NADH molecules and
two molecules of BPG,
each with one
high-energy phosphate
bond.

Isomerase

CH2OH
Phosphoenolpyruvate

45. The 6-carbon molecule


is split into two 3-carbon
moleculesone G3P,
another that is converted
into G3P in another
reaction.

Aldolase

CH2

Fructose
6-phosphate

Electron Transport Chain


Chemiosmosis

1. Phosphorylation of
glucose by ATP.

Glucose

NADH

Fructose
1,6-bisphosphate

ATP

O
C

CH2
O

Pyruvate

Glycolysis

CH3

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Without oxygen
Pyruvate

H2 O

O2

With oxygen
NAD+

CO2

NADH

NADH

Acetaldehyde

ETC in mitochondria
Acetyl-CoA

NAD+

NADH

Lactate

NAD+

Krebs
Cycle
Ethanol

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Glycolysis

Pyruvate Oxidation
NADH
Krebs
Cycle

Electron Transport Chain


Chemiosmosis

Pyruvate Oxidation: The Reaction


Pyruvate

Pyruvate

O
C
O
C
O
CH 3

CO2

NADH
CoA

Acetyl Coenzyme A

Acetyl Coenzyme A

NAD+

CoA

C
O
CH3

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Glycolysis

Pyruvate Oxidation

NADH
FADH2

Krebs
Cycle

CoA(Acetyl-CoA)

4-carbon
molecule
(oxaloacetate)

ATP

Electron Transport Chain


Chemiosmosis

CoA

6-carbon molecule
(citrate)

NADH

NAD +
NADH

NAD+

CO2
Pyruvate from glycolysis is
oxidized Krebs Cycle into an
acetyl group that feeds into the
Krebs cycle. The 2-C acetyl group
combines with 4-C oxaloacetate to
produce the 6-C compound citrate
(thus this is also called the citric
acid cycle). Oxidation reactions
are combined with two
decarboxylations to produce
NADH, CO2, and a new 4-carbon
molecule. Two additional
oxidations generate another
NADH and an FADH2 and
regenerate the original 4-C
oxaloacetate.

4-carbon
molecule

Krebs Cycle

5-carbon
molecule
NAD+

FADH2

NADH
FAD
CO2
4-carbon
molecule

4-carbon
molecule

ATP

ADP +

10

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Glycolysis
1. Reaction 1: Condensation
23. Reactions 2 and 3: Isomerization

Pyruvate Oxidation

4. Reaction 4: The first oxidation


5. Reaction 5: The second oxidation

NADH
Krebs
Cycle

FADH2

ATP

6. Reaction 6: Substrate-level phosphorylation


7. Reaction 7: The third oxidation

Electron T ransport Chain


Chemiosmosis

89. Reactions 8 and 9: Regeneration of


oxaloacetate and the fourth oxidation

Krebs Cycle: The Reactions

Malate (4C)
COO
HO CH

OC

CH2

COO

CH3 C S

Citrate (6C)
COO

CoA-SH

NAD+

Oxaloacetate (4C)
COO

NADH

Acetyl-CoA
O CoA

CH2

Citrate
synthetase

HO C COO

Malate
dehydrogenase

CH2

CH2
COO

COO
2

H2O

Aconitase
3

8 Fumarase

Isocitrate (6C)

Fumarate (4C)
COO

COO

CH

CH2

HC COO

HC

COO

HO CH
COO

FADH2
FAD

Succinate
dehydrogenase

Isocitrate
dehydrogenase 4

Succinate (4C)

NAD+

CO2

COO

NADH

CH2

-Ketoglutarate (5C)
CoA-SH
Succinyl-CoA
synthetase
GTP

ADP

6
GDP + Pi

CO2

COO
CH2
CH2
C O

ATP

COO

Succinyl-CoA (4C)

S CoA

CH2

-Ketoglutarate
dehydrogenase
5
CoA-SH

COO

CH2

CH2
CO

NAD+
NADH

COO

11

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Glycolysi s

Pyruvate Oxidatio n

Krebs
Cycle

ATP

Electron Transport Chain


Chemiosmosis

H++
H

Mitochondrial matrix
NADH dehydrogenase
NADH + H+

Cytochrome
oxidase complex

bc1 complex

2H+ + 1/2O2

NAD+

ATP

ATP
synthase

ADP + Pi

H2O

FADH2
2 e FAD
22 e

22 e
Q

Inner
mitochondrial
membrane

C
H+

H+

H+

H+

Intermembrane space

a. The electron transport chain

b. Chemiosmosis
12

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H+

Mitochondrial
matrix

ATP

ADP + Pi
Catalytic head

Stalk

Rotor

Intermembrane
space

H+

H+

H+

H+

H+

H+
13

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Glycolysis
NADH

Glucose
Pyruvate

Pyruvate
Oxidation

NADH

CO2

Acetyl-CoA

NADH

CO2
Krebs
Cycle

H+
32 ATP

FADH2

2 ATP

e
H2O

2H+
+
1/ O
2 2

Q
C
H+

H+
H+

14

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Glucose
2 ATP

ATP

ATP

Glycolysis
Pyruvate

NADH

Chemiosmosis

Pyruvate oxidation

Krebs
Cycle

NADH

NADH

ATP

ATP

15

ATP
Chemiosmosis

FADH2

ATP

Total net ATP yield = 32


(30 in eukaryotes)
15

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Glycolysis
Glucose

ADP
Activates

Fructose 6-phosphate

Phosphofructokinase

Inhibits

Inhibits

Fructose 1,6-bisphosphate

Pyruvate

Pyruvate Oxidation
Pyruvate dehydrogenase
ATP

Acetyl-CoA

Inhibits

Krebs
Cycle

Citrate
NADH

Electron Transport Chain


and
Chemiosmosis

16

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Alcohol Fermentation in Yeast


H

Glucose
2 ADP

2 ATP

G
L
Y
C
O
L
Y
S
I
S

OH

CH3
2 NAD+

2 Ethanol

2 NADH
H
C

CO2
2 Pyruvate

CH3

CH3
2 Acetaldehyde

Lactic Acid Fermentation in Muscle Cells


O

Glucose
2 AD P

2 ATP

O
C

CH3

G
L
Y
C
O
L
Y
S
I
S

2 Pyruvate

2 NAD+

OH

CH3
2 Lactate

2 NADH

17

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HO

HO
Urea

C
H2N
H
H

C
C
C

H
H

NH3

C
HO

O
HO

Glutamate

-Ketoglutarate
18

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Fatty acid C C C

O
OH

ATP

CoA

AMP + PPi

Fatty acid C C C CoA

FAD

Fatty acid
2C shorter

FADH2
O

Fatty acid C C C CoA

H2O

HO

Fatty acid C C C CoA

NAD+
CoA

NADH
H

Fatty acid C C C CoA

H
Acetyl-CoA

Krebs
Cycle

19

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Macromolecule
degradation

Nucleic acids

Proteins

Polysaccharides

Lipids and fats

Cell building blocks

Nucleotides

Amino acids

Sugars

Fatty acids

Glycolysis

-oxidation

Deamination
Oxidative respiration
Pyruvate

Acetyl-CoA

Krebs
Cycle

Ultimate metabolic products

NH3

H2O

CO2
20

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