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Metabolic Pathways for

Carbohydrates
Metabolism and Cell Structure
ATP and Energy

Copyright © 2007 by Pearson Education, Inc.


Publishing as Benjamin Cummings

1
Metabolism

Metabolism involves
▪ Catabolic reactions
that break down
large, complex
molecules to
provide energy and
smaller molecules.
▪ Anabolic reactions
that use ATP
energy to build
larger molecules.

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Stages of Metabolism
Catabolic reactions are organized as
Stage 1: Digestion and hydrolysis break down
large molecules to smaller ones that
enter the bloodstream.
Stage 2: Degradation breaks down molecules to
two- and three-carbon compounds.
Stage 3: Oxidation of small molecules in the citric
acid cycle and electron transport provide
ATP energy.

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Stages of Metabolism
Catabolic reactions:
Stage 1: Digestion and
hydrolysis
break down large
molecules to smaller
ones that enter the
bloodstream.

Stage 2: Degradation
Further breaking and
some oxidation of
molecules to 2 & 3-
carbon compounds.

Stage 3: Oxidation
of small molecules to
CO2 & H2O in the citric
acid cycle and electron
transport provides
energy for ATP
synthesis. 4
Cell Structure
Metabolic reactions occur in specific sites within cells.

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Cell Components and Function

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ATP and Energy

Adenosine triphosphate (ATP)


▪ Is the energy form stored in cells.
▪ Is obtained from the oxidation of food.
▪ Consists of adenine (nitrogen base), a ribose sugar,
and three phosphate groups.
▪ Requires 7.3 (31 kJ) per mole to convert ADP + Pi
to ATP.

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ATP and Energy

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Hydrolysis of ATP

▪ The hydrolysis of ATP to ADP releases 7.3 kcal (31


kJ/mole).

ATP ADP + Pi + 7.3 kcal (31 kJ/mole)

▪ The hydrolysis of ADP to AMP releases 7.3 kcal (31


kJ/mole).

ADP AMP + Pi + 7.3 kcal (31 kJ/mole)

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Hydrolysis of ATP to ADP and ADP to
AMP

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ATP and Muscle Contraction
Muscle fibers
▪ Contain the protein fibers actin and myosin.
▪ Contract (slide closer together) when a nerve
impulse increases Ca2+.
▪ Obtain the energy for contraction from the
hydrolysis of ATP.
▪ Return to the relaxed position as Ca2+ and ATP
decrease.

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ATP and Muscle Contraction

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Learning Check

Match the following:


1) ATP 2) ADP + Pi

A. Used in anabolic reactions.


B. The energy-storage molecule.
C. Coupled with energy-requiring reactions.
D. Hydrolysis products.

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Solution

Match the following:


1) ATP 2) ADP + Pi

A. 1 Used in anabolic reactions


B. 1 The energy-storage molecule.
C. 1 Coupled with energy-requiring reactions.
D. 2 Hydrolysis products.

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Metabolic Pathways for
Carbohydrates

Important Coenzymes in
Metabolic Pathways

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15
Coenzyme NAD+
NAD+ (nicotinamide adenine dinucleotide)
▪ Participates in reactions that produce a carbon-
oxygen double bond (C=O).
▪ Is reduced when an oxidation provides 2H+ and 2e-.

Oxidation O
||
CH3—CH2—OH CH3—C—H + 2H+ + 2e-
Reduction
NAD+ + 2H+ + 2e- NADH + H+

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Structure of Coenzyme NAD+
NAD+
▪ Is nicotinamide
adenine
dinucleotide.
▪ Contains ADP,
ribose, and
nicotinamide.
▪ Reduces to NADH
when the
nicotinamide group
accepts H+ and 2e-
.
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Coenzyme FAD

FAD (flavin adenine dinucleotide)


▪ Participates in reactions that produce a carbon-carbon
double bond (C=C).
▪ Is reduced to FADH2.

Oxidation
—CH2—CH2— —CH=CH— + 2H+ + 2e-

Reduction
FAD + 2H+ + 2e- FADH2

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Structure of Coenzyme FAD
FAD
▪ Is flavin adenine
dinucleotide.
▪ Contains ADP
and riboflavin
(vitamin B2).

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Coenzyme A

Coenzyme A.
▪ Consists of vitamins B3, pantothenic acid, and ADP.
▪ Activates acyl groups such as the two-carbon acetyl
group for transfer.

O O
|| ||
CH3—C— + HS—CoA CH3—C—S—CoA

acetyl group acetyl CoA

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Structure of Coenzyme A

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Learning Check

Match the following:


1) NAD+ 2) FAD 3) NADH + H+
4) FADH2 5) Coenzyme A

A. Coenzyme used in oxidation of carbon-oxygen


bonds.
B. Reduced form of flavin adenine dinucleotide.
C. Used to transfer acetyl groups.
D. Contains riboflavin.
E. The coenzyme after C=O bond formation.
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Solution

Match the following:


1) NAD+ 2) FAD 3) NADH + H+
4) FADH2 5) Coenzyme A

A. 1 Coenzyme used in oxidation of carbon-oxygen


bonds.
B. 4 Reduced form of flavin adenine dinucleotide.
C. 5 Used to transfer acetyl groups.
D. 2 Contains riboflavin.
E. 3 The coenzyme after C=O bond formation.

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Metabolic Pathways for Carbohydrates

Digestion of Carbohydrates
Glycolysis: Oxidation of Glucose

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Stage 1: Digestion of Carbohydrates
In Stage 1, the digestion of carbohydrates
▪ Begins in the mouth where salivary amylase breaks
down polysaccharides to smaller polysaccharides
(dextrins), maltose, and some glucose.
▪ Continues in the small intestine where pancreatic
amylase hydrolyzes dextrins to maltose and glucose.
▪ Hydrolyzes maltose, lactose, and sucrose to
monosaccharides, mostly glucose, which enter the
bloodstream for transport to the cells.

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Digestion of Carbohydrates

26

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Stage 2: Glycolysis

Stage 2: Glycolysis
▪ Is a metabolic
pathway that uses
glucose, a digestion
product.
▪ Degrades six-carbon
glucose molecules to
three-carbon. pyruvate
molecules.
▪ Is an anaerobic (no
oxygen) process.

27
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Glycolysis: Energy-Investment
In reactions 1-5 of glycolysis,
▪ Energy is required to add phosphate groups to
glucose.
▪ Glucose is converted to two three-carbon molecules.

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Glycolysis: Energy Investment

1
3

5 5
2

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Glycolysis: Energy-Production
In reactions 6-10 of glycolysis, energy is generated as
▪ Sugar phosphates are cleaved to triose phosphates.
▪ Four ATP molecules are produced.

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Glycolysis: Reactions 6-10

6
8 10

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Glycolysis: Overall Reaction
In glycolysis,
▪ Two ATP add phosphate to glucose and fructose-6-
phosphate.
▪ Four ATP are formed in energy-generation by direct
transfers of phosphate groups to four ADP.
▪ There is a net gain of 2 ATP and 2 NADH.

C6H12O6 + 2ADP + 2Pi + 2NAD+


Glucose
2C3H3O3- + 2ATP + 2NADH + 4H+
Pyruvate
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Regulation of Glycolysis
Glycolysis is regulated by three enzymes,
▪ Reaction 1 Hexokinase is inhibited by high levels of
glucose-6-phosphate, which prevents the
phosphorylation of glucose.
▪ Reaction 3 Phosphofructokinase, an allosteric
enzyme, is inhibited by high levels of ATP and
activated by high levels of ADP and AMP.
▪ Reaction 10 Pyruvate kinase, another allosteric
enzyme is inhibited by high levels of ATP or acetyl
CoA.

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Learning Check
In glycolysis, what compounds provide phosphate
groups for the production of ATP?

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Solution
In glycolysis, what compounds provide phosphate
groups for the production of ATP?
In reaction 7, phosphate groups from two
1,3-bisphosphoglycerate molecules are transferred to
ADP to form two ATP.
In reaction 10, phosphate groups from two
phosphoenolpyruvate molecules are used to form two
more ATP.

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Metabolic Pathways for Carbohydrates

Pathways for Pyruvate

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Pyruvate: Aerobic Conditions

Under aerobic conditions (oxygen present),


▪ Three-carbon pyruvate is decarboxylated.
▪ Two-carbon acetyl CoA and CO2 are produced.

O O pyruvate
|| || dehydrogenase
CH3—C—C—O- + HS—CoA + NAD+
pyruvate
O
||
CH3—C—S—CoA + CO2 + NADH
acetyl CoA
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Pyruvate: Anaerobic Conditions
Under anaerobic conditions (without oxygen),
▪ Pyruvate is reduced to lactate.
▪ NADH oxidizes to NAD+ allowing glycolysis to continue.

O O lactate
|| || dehydrogenase
CH3—C—C—O- + NADH + H+
pyruvate
OH O
| ||
CH3—CH—C—O- + NAD+
lactate
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Lactate in Muscles

During strenuous exercise,


▪ Oxygen in the muscles is depleted.
▪ Anaerobic conditions are produced.
▪ Lactate accumulates. OH

C6H12O6 + 2ADP + 2Pi 2CH3–CH–COO- + 2ATP
glucose lactate
▪ Muscles tire and become painful.
After exercise, a person breathes heavily to repay the
oxygen debt and reform pyruvate in the liver.

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Fermentation

Fermentation
▪ Occurs in anaerobic microorganisms such as yeast.
▪ Decarboxylates pyruvate to acetaldehyde, which is
reduced to ethanol.
▪ Regenerates NAD+ to continue glycolysis.
O OH
|| |
CH3—C—COO- + NADH + H+ CH3—CH2 + NAD+ + CO2

pyruvate ethanol

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Pathways for Pyruvate

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Learning Check

Match the following terms with the descriptions


1) Catabolic reactions 2) Coenzymes
3) Glycolysis 4) Lactate

A. Produced during anaerobic conditions.


B. Reaction series that converts glucose to pyruvate.
C. Metabolic reactions that break down large
molecules to smaller molecules + energy.
D. Substances that remove or add H atoms in
oxidation and reduction reactions.

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Solution

Match the following terms with the descriptions:


1) Catabolic reactions 2) Coenzymes
3) Glycolysis 4) Lactate

A. 4 Produced during anaerobic conditions.


B. 3 Reaction series that converts glucose to
pyruvate.
C. 1 Metabolic reactions that break down large
molecules to smaller molecules + energy.
D. 2 Substances that remove or add H atoms in
oxidation and reduction reactions.
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Metabolic Pathways for Carbohydrates

Glycogen Metabolism

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Glycogenesis
Glycogenesis
▪ Stores glucose by converting glucose to glycogen.
▪ Operates when high levels of glucose-6-phosphate
are formed in the first reaction of glycolysis.
▪ Does not operate when energy stores (glycogen)
are full, which means that additional glucose is
converted to body fat.

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Diagram of Glycogenesis

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Formation of Glucose-6-Phosphate
In glycogenesis
▪ Glucose is initially converted to glucose-6-
phosphate using ATP.

glucose-6-phosphate

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Formation of Glucose-1-Phosphate
Glucose-6-phosphate is converted
to glucose-1-phosphate.

glucose-6-phosphate glucose-1-phosphate

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UDP-Glucose
UTP activates glucose-1-phosphate to
form UDP-glucose and pyrophosphate
(PPi).

UDP-glucose

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Glycogenesis: Glycogen

▪ The glucose in UDP-glucose adds to glycogen.


UDP-Glucose + glycogen glycogen-glucose + UDP

▪ The UDP reacts with ATP to regenerate UTP.


UDP + ATP UTP + ADP

50
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Glycogenolysis
In glycogenolysis
▪ Glycogen is broken
down to glucose.
▪ Glucose molecules
are removed one by
one from the end of
the glycogen chain to
yield glucose-1-
phosphate.

51
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Glycogenolysis
Glycogenolysis
▪ Is activated by glucagon (low blood glucose).
▪ Bonds glucose to phosphate to form glucose-1-
phosphate.
glycogen-glucose + Pi
glycogen + glucose-1-phosphate

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Isomerization of Glucose-1-phosphate

▪ The glucose-1-phosphate isomerizes to glucose-6-


phosphate, which enters glycolysis for energy
production.

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Glucose-6-phosphate

Glucose-6-phosphate
▪ Is not utilized by brain and skeletal muscle because
they lack glucose-6-phosphatase.
▪ Hydrolyzes to glucose in the liver and kidney, where
glucose-6-phosphatase is available providing free
glucose for the brain and skeletal muscle.

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Learning Check

Match each description with


1) Glycogenesis 2) Glycogenolysis

A. Activated by low levels of blood glucose.


B. Converts glucose-1-phosphate to glucose-6-
phosphate.
C. Activated by high levels of glucose-6-phosphate.
D. Glucose + UTP UDP-glucose + PPi

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Solution

Match each description with:


1) Glycogenesis 2) Glycogenolysis

A. 2 Activated by low levels of blood glucose.


B. 2 Converts glucose-1-phosphate to glucose-6-
phosphate.
C. 1 Activated by high levels of glucose-6-phosphate.
D. 1 Glucose + UTP UDP-glucose + PPi

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Chapter 22 Metabolic Pathways for
Carbohydrates
22.8
Gluconeogenesis: Glucose Synthesis

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Utilization of Glucose
Glucose
▪ Is the primary
energy source for
the brain, skeletal
muscle, and red
blood cells.
▪ Deficiency can
impair the brain and
nervous system.

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Gluconeogenesis: Glucose Synthesis

Gluconeogenesis is
▪ The synthesis of glucose from carbon atoms of
noncarbohydrate compounds.
▪ Required when glycogen stores are depleted.

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Gluconeogenesis: Glucose Synthesis

60
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Gluconeogenesis: Glucose Synthesis

In gluconeogenesis,
▪ Glucose is synthesized from noncarbohydrates such as
lactate, some amino acids, and glycerol after they are
converted to pyruvate or other intermediates.
▪ Seven reactions are the reverse of glycolysis and use
the same enzymes.
▪ Three reactions are not reversible.
Reaction 1 Hexokinase
Reaction 3 Phosphofructokinase
Reaction 10 Pyruvate kinase

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Gluconeogenesis: Pyruvate to
Phosphoenolpyruvate
▪ Pyruvate adds a carbon to form oxaloacetate by two
reactions that replace the reverse of reaction 10 of
glycolysis.
▪ Then a carbon is removed and a phosphate added to
form phosphoenolpyruvate.

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Phosphoenolpyruvate to Fructose-1,6-
bisphosphate

▪ Phosphoenolpyruvate is converted to fructose-1,6-


bisphosphate using the same enzymes in glycolysis.

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Glucose Formation
Glucose forms when
▪ A loss of a phosphate from fructose-1,6-bisphosphate
forms fructose-6-phosphate and Pi.
▪ A reversible reaction converts fructose-6-phosphate to
glucose-6-phosphate.
▪ A phosphate is removed from glucose-6-phosphate.

64
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Cori Cycle

The Cori cycle


▪ Is the flow of lactate and glucose between the muscles
and the liver.
▪ Occurs when anaerobic conditions occur in active muscle
and glycolysis produces lactate.
▪ Operates when lactate moves through the blood stream
to the liver, where it is oxidized back to pyruvate.
▪ Converts pyruvate to glucose, which is carried back to
the muscles.

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Pathways for Glucose

are derived from

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66
Regulation of Glycolysis and
Gluconeogenesis

Regulation occurs as
▪ High glucose levels and insulin promote glycolysis.
▪ Low glucose levels and glucagon promote
gluconeogenesis.

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Regulation of Glycolysis and
Gluconeogenesis
TABLE 22.2

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Learning Check

Identify each process as:


1) glycolysis 2) glycogenesis
3) glycogenolysis 4) gluconeogenesis

A. The synthesis of glucose from noncarbohydrates.


B. The breakdown of glycogen into glucose.
C. The oxidation of glucose to two pyruvate.
D. The synthesis of glycogen from glucose.

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Solution

Identify each process as:


1) glycolysis 2) glycogenesis
3) glycogenolysis 4) gluconeogenesis

A. 4 The synthesis of glucose from


noncarbohydrates.
B. 3 The breakdown of glycogen into glucose.
C. 1 The oxidation of glucose to two pyruvate.
D. 2 The synthesis of glycogen from glucose.

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