Carbohydrates

of Physiologic
Significance
Chapters 3, 26

Mary E. Balliett, D.C. 1

References
 Dr. Michael King’s Site:
• www.themedicalbiochemistrypage.org
 Dr. June Steinberg’s Site:
• : http://www2.nl.edu/jste/carbohyd.htm
 http://web.virginia.edu/Heidi/chapter7/ch
p7.htm

Mary E. Balliett, D.C. 2

Introduction
 Physiologically
carbohydrates are
used for:
• Energy
• Storage of energy
• Cell Adhesion
molecules

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Chemistry

 Contain C:H:O in 1:2:1 ratio

 Synthesized from CO2 and H2O by
photosynthesis in plants
• Name is derived from the hydrate of carbon
• Abbreviated CH2O

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Classification

 Monosaccharides
• (subdivided by # carbons)
 Disaccharides
• (maltose, sucrose, lactose)
 Oligosaccharides
• (3-10 monosaccharides)
 Polysaccharides
• (>10, starch, dextrin)
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http://chemistry2.csudh.edu/rpendarvis/monosacch.html

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Categorization of
Monosaccharides
1. Functional group
 Aldehyde
 Ketone
2. Stereoisomers
3. Number of carbons
4. Ring Structure

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Functional Group
 If functional group is  If the functional
an aldehyde the group is a ketone the
monosaccharide is monosaccharide is
termed an ALDOSE termed a KETOSE

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Aldose-Ketose Isomerism

 Isomers have the same

molecular formula
• Fructose is a ketose
• Glucose is an aldose

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Stereoisomers

 Presence of chiral carbon

(asymmetric carbon attached to
four different atoms/groups)
 Total Number of stereoisomers
• is calculated by 2n.
• Where n = # of chiral carbons

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Calculating chiral carbons
 Number of chiral
carbons is:
• For Aldose:
• Total carbons - 2 = n
• For Ketose:
• Total carbons – 3 = n
 Example: Glucose
• Aldose: 6 – 2 = 4 = n
• 2n = 16

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Total Stereoisomers
are divided into 2 groups
 Half of the stereoisomers will rotate plane polarized
light to the right and half to the left.
 Termed D and L

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Only D isomers are
Naturally occurring
 The chiral carbon
furthest from the
functional group
(aldehyde or ketone)
is conventionally
written to the RIGHT

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Classifying by:
Number of Carbons
# Carbons Group Name
3 Triose
4 Tetrose
5 Pentose
6 Hexose
9 Nonose

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Triose: Aldose
 D-glyceraldehyde  L-glyceraldehyde

Chiral carbons = 1;
Stereoisomers = 2;
Naturally occurring = 1

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Triose: Ketose
 Dihydroxyacetone

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 Tetrose: aldose

Chiral carbons =
Stereoisomers =
Naturally occurring =

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 Pentose: Aldose

Chiral carbons =
Stereoisomers =
Naturally occurring =

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Pentose: Ketose
 D-ribulose

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Hexose: Aldose

Chiral carbons =
Stereoisomers =
Naturally occurring =

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Hexose: Ketose

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Nonose: Sialic Acid

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Ring Formation
 Hemiacetal
• Aldehyde reacts with
one alcohol group to
form an acetal bond
and the
monosaccharide forms
a ring with the same
number in the ring as
the original number of
carbons

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Ring Formation
 Hemiketal
• Ketone reacts with one
alcohol group to form a
hemiketal bond and the
monosaccharide forms
a ring 1 number less
than the original
numbers of carbons

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Ring Structures

 Pyranose: 6 member ring  Furanose: 5 member ring

 Glucose is 99% pyranose

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 Anomers

 Ring Structure can open and re-close

• Allow rotation at Carbon #1
• Termed Mutorotation
 Carbon #1 termed ANOMERIC carbon

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Benedict’s solution and
Reducing Sugars
 The presence of
an anomeric
carbon allows the
sugar to “reduce”
Benedict’s solution
and turn it from
blue to red
• Termed a
“reducing
sugar”

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Alpha and Beta Anomers
 alpha: OH group
drawn down on C#1
 beta: OH group
drawn up on C#1

 Dextrose
• mixture of alpha and
beta D-glucose

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Alpha D-glucose
 Anomeric OH is
DOWN

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Beta D-glucose
 Anomeric OH is
UP
 Preferred form
due to steric
hindrance

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Epimers
of Glucose
 Isomers differing as
a result of variations
of -OH and -H on
carbon atoms 2, 3, 4
 Mannose
• epimer at C2
 Galactose
• epimer at C4

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Mary E. Balliett, D.C. 32
Sucrose

• Composed of:
• Glucose and fructose
• Bond:
• alpha 1->2 beta
glycosidic bond
• Food Source:
• table sugar (cane
sugar)
• Notes:
• non-reducing sugar

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Lactose
• Composed of:
• Galactose and
glucose
• Bond:
• beta 1-> 4 glycosidic
bond
• Food Source:
• Milk sugar
• Notes:
• Only animal source
of carbohydrate

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Maltose
• Composed of:
• Glucose and glucose
• Bond:
• alpha 1->4 glycosidic
bond
• Food Source:
• Malt sugar
• Notes:
• Formed by digestion
in mouth of starch
(amylose)

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Mary E. Balliett, D.C. 36
Polysaccharides

 Starch
 Glycogen
 Inulin
 Cellulose

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Starch

 Polymer of glucose
termed glucosan
 Most important food
source
• (cereals, potatoes,
vegetables)
 Amylose &
amylopectin

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Amylose
 non-branching alpha 1-> 4 glycosidic
bonds

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Amylopectin
 non-branching alpha 1->4 glycosidic
bonds
 branching alpha 1->6 glycosidic bonds

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Glycogen

 non-branching alpha
1->4 glycosidic
bonds
 branching alpha 1->6
glycosidic bonds
• More branching than
amylopectin

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Location & Function
of Glycogen
 Location: Liver and Muscle
 Function: Storage form of glucose
 Note: once the glycogen stores have
been met, all other glucose will be
converted to fatty acids and stored as
triacylglycerols

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Cellulose

 non-branching beta 1-> 4 glycosidic

bonds

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Fiber
 Unable to be digested by humans
• can be fermented by bacteria in GI tract
• especially in ruminants (like cows)
 Found in plant cell walls

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Types of Fiber
 Insoluble  Soluble
• Cellulose • Beta-glucans
• Hemicellulose  Gives feeling of
 Gives stool “bulk” “fullness” after eating
 Decreases bowel  Protects against
transit time cardiovascular
disease

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RDA Fiber
 Women: 25 grams/day
 Men: 38 grams/day

 Approximately 5 serving (cups) of fruits

and/or vegetables

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Inulin

 Polymer of fructose
termed fructosan
 Starch found in
tubers, roots of
artichokes, dahlias,
dandelions, onions,
bananas

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Fructooligosaccharides
 Provide “food” for good intestinal bacteria
 A carbohydrate that selectively supports the
growth and/or activity of Bifidobacteria and
Lactobacilli species is termed a prebiotic
 May act as a natural approach to antibiotic
therapy since ineffective fuel source for most
pathogenic species of bacteria

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Mary E. Balliett, D.C. 49
Cell junctions contain
glycosaminoglycans

http://www.steve.gb.com/images/science/cell_adhesion_summary.png

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Glycosaminoglycans

 Long unbranched polysaccharides

• containing repeating modified disaccharide
units
 Disaccharide units contain:
• Amino sugar
• N-acetyl glucosamine (GlcNAc) or
• N-acetyl galactosamine (GalNAc)
• Uronic Acid
• Glucoronate or Iduronate

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Amino Sugars
Glucosamine N-Acetyl-Galactosamine

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Uronic Acids

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Glycosaminoglycans
AKA GAG’s
The general structures of the glycosaminoglycans (GAGs) consist of a hexosamine and a
uronic acid residue (except keratan sulfate where uronic acid is replaced by galactose).

Proteoglycan Amino Sugar Uronic Acid Location

(GAG)
Hyaluronic acid Glucosamine Glucuronic Joint and ocular
fluids
Chondroitin sulfate Galactosamine Glucuronic Cartilage, tendons,
bone
Dermatan sulfate Galactosamine Iduronic Skin, valves, blood
vessels
Heparan sulfate Glucosamine Iduronic Cells surfaces
Heparin Glucosamine Iduronic Mast cells, liver
Keratan sulfate Glucosamine None (galactose) Cartilage, cornea

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http://web.virginia.edu/Heidi/chapter7/chp7.htm

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Proteoglycans
 www.themedicalbiochemistrypage.com
 GAG linked to core protein
 Have “bottle-brush” appearance

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