Dietary Sources of Carbohydrates

Starch: the nutritional

store of glucose in
plants.

(30)
(1)
-1,4 & -1,6 glycosidic
linkages
1
Branched

6
4

glu

1 4

Unbranched

3
glu

Disaccharides

2 Forms of Starch (nutritional reservoir in plants)

-1,4 glycosidic linkages

A major source of
dietary glucose.

(Most abundant biomolecules

on earth)

glu

Similar to glycogen in
animal cells, but less
extensive branching
in starch.

2
fru

glu

glu

gal

glu

Monosaccharides
gal
glu

fru

Carbohydrate oxidation is the central energy yielding pathway in most cells.

Initial Digestion of Carbohydrates

b) Brush Border of the Mucosal Epithelium
Final hydrolysis of di- and oligosaccharides to monosaccharides.
Catalyzed by enzymes on the surface of the small intestinal epithelial
cells. Excess capacity for digestion of starch and sucrose.

Only monosaccharides can be absorbed into intestinal epithelial cells.

Absorption of Monosaccharides
Monosaccharides are absorbed from the brush border membrane of
the intestinal epithelial cells and ultimately into the bloodstream via
the actions of specific transport proteins.
Rate of monosaccharide absorption is enhanced via microvilli (increase
surface area) and the existence of specific transport proteins.

Luminal; Brush
border membrane
Microvilli

Contraluminal
membrane

Na-dependent
Active
Transport

Facilitated
Diffusion
Na-independent

Sugar moves from small intestine

intestinal epithelial cell

Facilitated
Diffusion
Na-independent

bloodstream

Stage 1
-2 ATP

Stage 2
+4 ATP

Stage 2
+4 ATP

2 NAD+

2 NAD+
11
Lactate (2)

Glycolysis: Stage 1
Initial Strategy: Trap glucose in the cell and convert it to a compound
that can be cleaved into phosphorylated 3-carbon units.
1st Reaction: Glucose enters cell and is phosphorylated to glucose
6-phosphate, a negatively charged molecule which is trapped inside
the cell.
6

2nd Reaction: the isomerization of glucose 6-phosphate to fructose

6-phosphate.
Catalyzed by phosphoglucose isomerase.
6 membered
pyranose ring
6
5

5 membered
furanose ring
6

4
3

This reaction is readily reversible.

1
2

5
4

This reaction represents an example of a conversion of an

aldose to a ketose.

Open chain representation of the sugars.

1

Aldehyde

An aldehyde containing sugar.

Ketone

A ketone containing sugar.

3rd Reaction: Fructose 6-phosphate is phosphorylated by ATP to

form fructose 1,6-bisphosphate.
This is the second of the two priming reactions in glycolysis.
Catalyzed by phosphofructokinase (PFK; PFK1).
6

2
4

PFK is the major point of regulation in glycolysis. Rx is irreversible.

PFK is regulated allosterically.

4th Reaction: Cleavage of fructose 1,6-bisphosphate to glyceraldehyde

3-phosphate and dihydroxyacetone phosphate.
Represents cleavage of a hexose into two trioses.

1
2
3
4

1
2

5
6

5
6

Note: Reaction is readily reversible. It is pulled to the right via removal

of glyceraldehyde 3-phosphate via subsequent steps.
Only glyceraldehyde 3-phosphate is on the direct pathway of glycolysis.

5th Reaction: Isomerization of 3-carbon phosphorylated

sugars, catalyzed by triose phosphate isomerase.

Stage 1
-2 ATP

Stage 2
+4 ATP

2 NAD+
2 NAD+

2 NAD+
11
Lactate (2)

6th Reaction: Oxidation of glyceraldehyde 3-phosphate to

1,3-bisphosphoglycerate.
Aldehyde
group

1
2
3

NAD+dependent

Note: The mixed anhydride

has a very high free energy
of hydrolysis.
1
2

Mixed
anhydride

This is a mixed anhydride

of phosphoric acid and a
carboxylic acid.

The first of the two energy-conserving

reactions of glycolysis that will ultimately
yield ATP.

7th Reaction: First ATP-generating step. ATP is formed as the phosporyl

on the carboxyl group of 1,3-bisphosphoglycerate is transferred to ADP.
Substrate Level Phosphorylation

1
2
3

Note: The consequences of this reaction in

combination with the 6th reaction are:
1) An aldehyde is oxidized to a carboxylic
acid group.

1
2
3

2) NAD+ is concomitantly reduced to NADH.

3) ATP is formed from Pi and ADP.

8th Reaction: The phosphoryl group is shifted from the C-3 to the C-2
position of glycerate. Catalyzed by phosphoglycerate mutase.
Note: A mutase transfers a functional group from one position to
another on the same molecule.

9th Reaction: A dehydration reaction is which water is reversibly

removed from 2-phosphoglycerate to from phosphoenolpyruvate.
Catalyzed by enolase.
Large difference in the standard free energy of hydrolysis of the
phosphate group in the reactant versus the product.

10th Reaction: Transfer of a phosphoryl group from PEP to ADP

catalyzed by pyruvate kinase.
Irreversible; An important site of regulation in the liver.
The second substrate level phosphorylation.

11th Reaction: Reduction of pyruvate to lactate via the enzyme

lactate dehydrogenase.
Conversion of occurs under partially anerobic conditions, when
oxygen is limited (e.g., muscle during intense activity) OR in
certain tissues even when sufficient oxygen is present (retina,
brain, RBCs).
NADH required for this reaction is supplied
by the 6th reaction (the dehydrogenation of
glyceraldehyde 3-phosphate).

Importantly, under anaerobic conditions, the

regeneration of NAD+ by this step is
essential
for the continued functioning of glycolysis.

Entry of Other Monosaccharides into Glycolysis

D-Fructose: present in fruits; also can be generated by hydrolysis of

sucrose (yield fructose + glucose).
Note: In the liver hexokinase has a 20x higher affinity for glucose
compared to fructose. Since there is a lot of glucose present in this
organ, fructose is not principally metabolized by hexokinase, but
rather by the following pathway:

(2)

(1)

(1) Fructose intolerance results from a deficiency in fructose 1-phosphate

aldolase. Leads to an accumulation in fructose 1-phosphate and a depletion
of ATP and Pi. Pi depletion makes it impossible to generate more ATP
lowering levels even further. Causes cell damage.
(2) Fructosuria results from a deficiency in fructokinase. Fructose appears
in blood and urine. Relatively benign metabolic abnormality.

Conversion of Glucose to Fructose via Sorbitol

Aldose reductase reduces glucose to sorbitol, which is quite polar
and thus does not passively diffuse across membrane.
Also, its not a substrate for the glucose transporter.
Therefore its trapped inside cells.
Liver, ovaries, sperm, and seminal
vesicles contain the enzyme sorbitol
dehydrogenase.
Oxidizes sorbitol to fructose.
Fructose then enters glycolysis or
gluconeogenesis.

When glucose is elevated (e.g., diabetes) and if there is sufficient

NADPH, aldose reductase produces excess sorbitol.
Retina, lens, kidney, and nerve cells do not contain sorbitol
dehydrogenase and therefore sorbitol accumulates.
Causes a strong osmotic effect and cell swelling due to water retention.
Symptomalogy occurs (cataract formation, peripheral neuropathy, and
vascular problems).

No sorbitol
dehydrogenase.

Alcoholic Fermentation
The sequence of reactions from glucose to pyruvate is similar in all
organisms.
However, in yeast and several other microorganisms ethanol is
formed from pyruvate via the following 2 reactions:
Note: the CO2 produced via pyruvate
decarboxylation in Brewers yeast is
responsible for the carbonation of
champagne.

Absent in
Humans.

In baking the CO2 released when yeast

is mixed with a fermentable sugar
causes the dough to rise.
Present in humans.
partly responsible
for the oxidation of
ethanol.