BIOCHEMISTRY (LECTURE)

MODULE 8: Carbohydrates

Classifications of Carbohydrates:

Carbohydrate The simpler members of the

carbohydrate family are often referred
- Means “hydrate of carbon” and to as saccharides because of their
derives from the formula sweet taste (Latin: saccharum, “sugar”).
- Generally considered as The classification depends on the
substances made up of carbon, number of simple sugars they contain.
hydrogen and oxygen
- Polymers of ● Monosaccharides
polyhydroxyaldehydes and / or ○ Cannot be hydrolyzed
polyhydroxyketones, or further into simpler
compounds that yield them after forms
hydrolysis ● Disaccharides
○ Yield 2 molecules of
same or different
monosaccharide
units on hydrolysis
● Oligosaccharides
○ Yield 3-10 molecules of
monosaccharide
units on hydrolysis
Functions of Carbohydrates:
● Polysaccharides
1. Major source of energy ○ Yield more than 10
2. Carbohydrate storage in the form molecules of the same
of glycogen, provides a or different
short-term energy reverse monosaccharide
3. Supplies cabron atoms for the units on hydrolysis
synthesis of other biochemica ○ Homo- &
substances (proteins, lipids, and Heteropolysaccharide
nucleic acids) s
4. Forms part of the structural
framework of DNA and RNA
molecules MONOSACCHARIDE
5. Linked to lipids are structural - A carbohydrate that cannot be
components of cell membranes hydrolyzed to a simpler
6. Lined to proteins function in a carbohydrate
variety of cell-cell and - Building block of all
cell-molecule regulation carbohydrates
processes
- General formula of 𝐶𝑛(𝐻2𝑂)𝑛
(hydrates of C), where n is the
number of atoms and with one of
the carbons being the carbonyl
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MODULE 8: Carbohydrates

group of ether an aldehyde or a ● Galactose

ketone ○ Is synthesized from glucose
- Contains three to nine carbon in mammary glands for use
atoms in lactose (milk sugar) which
- The suffix –ose indicates that a is disaccharide consisting a
molecule is a carbohydrate, and glucose unit and a
the prefixes tri-, tetr-, pent- and galactose unit
so forth, indicate the number of ○ Sometimes called brain
carbon atoms in the chain sugar
Aldose

- A monosaccharide containing an Monosaccharides are classified

aldehyde group according to the number of carbon
atoms they contain:
Ketose
No. of Carbons Class of
- A monosaccharide containing an Monosaccharide
ketone group
3 triose

Common Examples: 4 tetrose

5 pentose
● Glucose
○ Known as grape sugar 6 hexose
○ From ripe fruits particularly
ripe grapes The presence of an aldehyde is
○ Also known as dextrose and indicated by the prefix aldo- and
blood sugar ketone by the prefix keto-. Trioses are
● Fructose simplest carbohydrate
○ Is known as levulose and monosaccharides.
fruit sugar
○ The sweetest tasting of all
sugars and found in many Examples of monosaccharides found in
fruits and is present in humans, classified according to the
honey number of carbons they contain:
● D-Ribose
○ A component of a variety of
complex molecules,
including ribonucleic acids
(RNA) and energy rich
compounds such as
adenosine and
triphosphate
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MODULE 8: Carbohydrates

DISACCHARIDE

- Composed of two
monosaccharide units joined by
glycosidic linkage between the
anomic carbon of one unit and
an -OH group of the other unit

Common Examples:

● Sucrose (table sugar)

○ The most abundant
disaccharide
● Lactose (milk sugar)
○ Major sugar found in milk
○ Accounts for 5-8% of
human milk and 4-6% of
cow’s milk
● Maltose (malt sugar)
○ Derives its name and
presence in a malt
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○ The is juice from sprouted ○ Composed of hundred of

barley and other cereal glucose molecules joined
grains together
○ A component of many types
Although disaccharides contain of foods, such as bread,
no carbonyl groups, they are pasta, potatoes, rice, corn
hydrolyzed to simple monosaccharides and peas
that contain an aldehyde or ketone. ● Glycogen
○ Also made by linking
together glucose molecules
OLIGOSACCHARIDES
○ Is used by animals to store
- Composed of six to ten sugar and provide energy
monosaccharide groups ● Cellulose
covalently bonded with each ○ Is synthesized, stored,
other modified and used as a
- Complete hydrolysis of an building material by plants
oligosaccharide produces ○ Most abundant of all the
monosaccharides polysaccharides
○ Tiny forces called hydrogen
bonds hold the glucose
POLYSACCHARIDES
molecules together, and the
- The most complex of all chains in close proximity
carbohydrates ○ Used in making papers, as
- Consist of large number of well as cotton in our clothes
monosaccharide units bonded and the wood in our houses
together by glycosidic bonds
- Can be hydrolyzed by enzymes or
by heating with strong acids to
yield monosaccharide

Common Examples:

● Starch
○ The energy storage
polysaccharide (storage
form for monosaccharides
and is used as an energy
source in cells) in plants
○ The main carbohydrate
found in the seeds and
roots of plants
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MODULE 8: Carbohydrates

Carbohydrates are storehouses ➔ Asymmetric Carbon Atom

of chemical energy. It can be ◆ Attached to four different
synthesized in green plants and algae atoms or groups
through photosynthesis, a process that ➔ Vant Hoff’s Rule
uses the energy from the sun to 𝑛
◆ The possible isomers (2 ) of
convert carbon dioxide and water into a given compound is
glucose and oxygen. determined by the number
Plants store glucose in the form of asymmetric carbon
of polysaccharides like starch and atoms (n)
cellulose. ➔ Reference C Atom
◆ Penultimate C atom, around
which mirror images are
found

Two types:

1. Enantiomers
- Are stereoisomers whose
molecules are
The energy stored in glucose non-superimposable mirror
bonds is released when glucose is images of each other
metabolized. The oxidation of glucose - Molecules with chiral center
bonds is released when glucose is
metabolized. The oxidation of glucose
is a multistep process that forms
carbon dioxide, water and a great deal
of energy. Although the metabolism of
lipids provides more energy per gram
than the metabolism of carbohydrates,
glucose is the preferred source when
burst of energy is needed during
exercise.

Glucose is soluble, so it can be

quickly and easily transported through
the bloodstream and tissues.

Stereoisomers

➔ Are isomers that have the same

molecular and structural
formulas but differ in the
orientation of atoms in space
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MODULE 8: Carbohydrates

2. Diastereomers - Vertical lines represent

- Are stereoisomers whose bonds projecting to the
molecules are not mirror rear (Dash)
images of each other - The carbon atom at the
intersection of the
horizontal and vertical lines
is not shown

Glyceraldehyde

- The simplest carbohydrate

- Exists in two isomeric forms that
are mirror images of each other:

These forms are stereoisomers of each

other Object & Mirror Images

- Glyceraldehyde is a chiral - Most monosaccharides exist in

molecule - it cannot
superimposed on its mirrored
image. The two mirror-image
forms of glyceraldehyde are
enantiomers of each other
be two forms: a “left handed” and
“right handed” form - same as two
hands

FISCHER PROJECTIONS

- Bonds are written in two

dimensional representation
showing the configuration of
tetrahedral stereocenters
- Horizontal lines represent
bonds projecting forward
(Wedge)
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MODULE 8: Carbohydrates
D, L Monosaccharides
According to the conventions
proposed by Fischer:
● D-monosaccharide
○ A monosaccharide that
when written as a Fischer
Projection, has the -OH on
its penultimate carbon on
the right
● L-monosaccharide
○ A monosaccharide that
when written as a Fischer
Projection, has the -OH on
its penultimate carbon on
the left
When a molecule has more than one
chiral carbon, each carbon can
possible be arranged in either the
right-hand or left-hand form, thus if
𝑛
there are n chiral carbons, there are 2
possible stereoisomers
Chiral Carbon
- Chiral molecules have the same
relationship to each other than
your left and right hands have
when reflected in a mirror
- Achiral objects can be
superimposed on the mirror
images - for example, drinking
glasses, spheres, and cubes
- Any carbon atom which is
connected to four different
groups will be chiral, and will
have two nonsuperimposable
mirror images; it is a chiral
carbon or a center of chirality
- If any of the two groups on
the carbon are the same,
the carbon atom cannot be
chiral
- Many organic compounds,
including carbohydrates,
contains more than one chiral
carbon
There is no correlation between D, L
and +, -
- In D and L you need to look at the
structure
- + and - are determined by using a
polarimeter
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MODULE 8: Carbohydrates

- Most commonly written with the

anomeric carbon on the right
and the hemiacetal oxygen to the
back right
- The designation β − means that
-OH on the anomeric carbon is
cis to the terminal − 𝐶𝐻2𝑂𝐻; α −
means that it is trans

HAWORTH PROJECTIONS

- Five and six membered

hemiacetals are represented as
planar pentagons or hexagons,
as the case may be viewed
through the edge
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MODULE 8: Carbohydrates

Haworth Projections (Cont’d) 2. α means that the -OH on the

anomeric carbon is on the side of
- A six-membered hemiacetal ring the ring opposite from the
is shown by the infix-pyran-
terminal -𝐶𝐻2𝑂𝐻
(pyranose)
- A five-membered hemiacetal ring 3. A six-membered hemiacetal ring
is shown by the infix -furan- is called a pyranose, and a
(furanose) five-membered hemiacetal ring is
- Five-membered rings are so close called a furanose
to being planar that Haworth
Projections are adequate to
represent furanoses
- For pyranoses, the six-membered
ring is more accurately
represented as a strain-free chair
conformation
Drawing Furanose & Pyranose Rings

Terminology of Carbohydrate - The remaining OH groups on the

Chemistry: ring point up or down depending
on the identity of the sugar
1. β means that the -OH on the
anomeric carbon is on the same
side of the ring as the terminal -
𝐶𝐻2𝑂𝐻
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MODULE 8: Carbohydrates
BIOCHEMISTRY (LECTURE)
MODULE 8: Carbohydrates

What happens if a sugar forms a cyclic

molecule?

● Cyclization of sugars takes place

due to interaction between
functional groups on distant
carbons, C1 to C5, to make a
cyclic hemiacetal
● Cyclization using C2 to C5 results
in hemiketal formation
● In both cases, the carbonyl
carbon is new chiral center and
becomes an anomeric carbon

Cyclic Structure

- Aldehydes and ketone react with

alcohols to form hemiacetals
- Cyclic hemiacetals form
readily when hydroxyl and
carbonyl groups are part of
the same molecule and
their interaction can form a
five or six-membered ring

- Monosaccharides have -OH and

C=O groups in the same molecule
and exist almost entirely as five to
six-membered cyclic hemiacetals
- Anomeric carbon are the
new stereocenter resulting
from cyclic hemiacetal
formation
- Anomers are carbohydrates
that differ in configuration
only at their anomeric
carbons
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MODULE 8: Carbohydrates

orientation of groups on carbons

1-5 of β-D-glucopyranose are up,
Chair Conformations
down, up, down and up
- For pyranoses, the six-membered
ring is more accurately
represented as a chair
conformation

- In both Haworth projections and

chair conformations, the
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MODULE 8: Carbohydrates

Chair is the most STABLE Oxidation

conformation.

Hydrogen is axial and larger

substituents are equatorial - less
opportunity for steric interactions.

Reactions of Monosaccharides

● Tautomerization or Enolization
● Reducing Properties
● Oxidation
● Reduction
● Dehydration
Reaction of Monosaccharides
● Formation of Esters
● Glycoside Formation - Reducing sugar is the one that
reduces an oxidizing agent.
Sugars the can be oxidized are
Enediol Formation called reducing sugars
- In mild alkaline solutions, - Oxidation of a cyclic
carbohydrates containing free hemiacetal form gives a
sugar group tautomerizes to lactone
form enediols, where 2 -OH - When the oxidizing agent is
groups are attached to Tollens solution, silver
double-bonded carbon precipitates as a silver
mirror
- If anomeric carbons are involved
in glycosidic linkage, there will be
a negative Tollens reagent test
- If another anomeric carbon is not
bonded and is free, there will be a
positive Tollens reagent test
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MODULE 8: Carbohydrates

Reduction of Monosaccharides Examples:

- Monosaccharides can be 1. Glucose–6-phosphate

reduced turning the carbonyl 2. Glucose-1-phosphate
group into an alcohol group
- The resultant product is a sugar - ATP donates the phosphate
alcohol moiety
- The products named by replacing - The hydroxyl group of anomeric
the -ose ending with -itol carbon of a carbohydrate can
- Glucose forms sorbitol join with a hydroxyl group of
(glucitol) another carbohydrate or some
- Mannose forms mannitol other compound to form a
- Fructose forms a mixture of glycoside and the bond so
mannitol and sorbitol formed is known as glycosidic
- Glyceraldehyde form bond
glycerol Eg. R-OH + HO-R’ → R-O-R’ + 𝐻2𝑂
- The non-carbohydrate moiety is
known as aglycone-phenol, sterol
Dehydration bases, 𝐶𝐻3𝑂𝐻, glycerol
- Glycosidic bond can be N-linked
or O-linked
- Glycoside is a molecule in
which a sugar is bound to
another functional group
via glycosidic bond

Furfurals condense with phenolic

compounds (α-naphthol) to form
colored products

- Basis of the “Molisch Test:

Formation of Esters

- Esterification of alcoholic groups

of monosaccharides with
phosphoric acid is a common
reaction in metabolism
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MODULE 8: Carbohydrates

Amino Sugars

- Amino groups are substituted for

hydroxyl groups of sugars
N & O Glycosidic Linkage

Biomedical Importance of Glycosides

● Cardiac Glycosides
○ Digoxin, Digitoxin Important derivatives of
■ Used in cardiac monosaccharides
insufficiency
● Amino Sugars
■ Contains steroids as
- Are formed by replacing the
aglycone component
hydroxyl group (C2 usually)
● Ouabain
of monosaccharides by
○ Sodium pump inhibitor
amino group
● Streptomycin - Most common amino
○ antibiotic sugars are glucosamine
● Phloridzin and galactosamine
○ Cause renal damage, - Glucosamine is
glycosuria present in Heparin,
■ Obtained from root & Hyaluronic acid and
bark of apple tree blood groups
■ Blocks the transport substances
of sugar across the - Galactosamine is
mucosal cells of small present in
intestine & also renal Chondroitin of
tubular epithelium cartilages and
tendons
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Deoxy Sugars
SUCROSE
- Oxygen of the hydroxyl group is (α-D-Glucopyranosyl-(1→2)-β-D-fructofuranose
removed to form decoy sugars
- Non-reducing and non-osazone
forming
- Important part of nucleic acids

LACTOSE
(β-D-Galactopyranosyl-(1→4)-α-D-glucopyranose

Disaccharides

- Is formed when the hemiacetal or

hemiketal group on one
monosaccharide reacts with one
of the hydroxyl groups on
another monosaccharide with MALTOSE
the elimination of water (α-D-Glucopyranosyl-(1→4)-α-D-glucopyranose
- Two monosaccharides combine
together by glycosidic linkage
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○ Two α-D-glucose units held

Reducing Disaccharides together by (α1→α1)
● Maltose glycosidic bond
○ 2 α-D-glucose units held
together by α(1→4) CONCEPT REVIEW
glycosidic bond
● Lactose What monosaccharide are obtained by
○ β-D-galactose & β the hydrolysis of each disccharide?
-D-glucose units held A. Sucrose
together by β(1→4) D-glucose & D-fructose
glycosidic bond B. Maltose
● Cellobiose two molecules of D-glucose
○ Two β-D-glucose units held C. Lactose
together by β(1→4) D-glucose & D-galactose
glycosidic bond
● Sucrose
○ α-D-glucose and β Polysaccharide
-D-fructose units held - Repeat units of monosaccharides
together by (α1→β2) or their derivatives held together
glycosidic bond (an invert by glycosidic bonds
sugar when hydrolyzed)
● Trehalose 2 main functions:

- Energy storage
- Structure
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MODULE 8: Carbohydrates

- Can either be ○ More branched than

homopolysaccharide or amylopectin linked by α(1→4)
heteropolysaccharide and a α(1→6)

Homopolysaccharides
● Cellulose
● Starch
○ Chief carbohydrate in
○ Consist of amylose (water
plants
soluble) & amylopectin
(water insoluble) ○ Made up of repeating units
■ Amylose of cellobiose
● 200-20,000 ○ Cannot be digested by
D-glucose units humans
held together by ● Inulin
α(1→4) glycosidic ○ Repeating β-D-fructose
linkages units liked by β(1→2)
■ Amylopectin ○ Acts as a marker for
● Branched chain glomerular filtration since it
● α(1→6) glycosidic is not synthesized,
bonds at metabolized but filtered
branches completely by glomerulus
● 20-30 glucose ● Dextrans
units per ○ Branched poly-α-D-glucose
branch ○ used in managing and
● Glycogen treating various clinical
○ Reserve carbohydrate in conditions, including
animals during hemorrhage, shock,
○ Stored in liver & muscle surgical procedures,
○ Contains primer protein: radiological imaging,
antithrombotic
Glycogenin
administration, and
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MODULE 8: Carbohydrates

ophthalmic relief of ○ GAGs are highly polar and

xerophthalmia attracts water
● Chitin ○ Useful to the body as a
○ Abundantly found in lubricant or as a shock
crustaceans (eg. lobsters, absorber
crabs, shrimps, insects)
○ Composed of N-acetyl 1. Hyaluronic Acid
glucosamine units joined by - Present in connective
β-1,4 glycosidic linkages tissues, tendons, synovial

Heteropolysaccharides

● Agar
○ Prepared from sea weeds
○ Contains galactose,
glucose, and other sugars
○ Used as supporting fluid and vitreous humor
medium for
immunodiffusion & 2. Heparin
immunoelectrophoresis - Anticoagulant
○ Agarose contains galactose - Bind and activate
combined with 3,6 Antithrombin III, which in
anhydrogalactose units turn activates Thrombin,
○ Agarose is used as matrix Factor X & Factor IX
for electrophoresis
● Mucopolysaccharides
○ Also known as
glycosaminoglycans (GAGs)
○ Most abundant
heteropolysaccharide in
the body
○ Are long unbranched
polysaccharides containing 3. Chondroitin Sulfate
a repeating disaccharide - Present in ground
unit substances of connective
○ The repeating unit (except tissues of cartilages, bones
for keratan) consists of an & tendons
amino acid sugar
(N-acetylglucosamine or
N-acetylgalactosamine)
along with a uronic sugar
(glucouronic acid and
iduronic acid) or galactose
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4. Keratan Sulfate 5. Dermatan Sulfate

- The only GAG without - Found in skin, blood vessels
Uronic acid unit and heart vessels
- Found in the cornea
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Blood Types & Monosaccharides chirality center farthest from the

carbonyl on the right side. An L
- Human blood is classified into 4 sugar has the OH group chirality
types: A, B, AB, and O center from the carbonyl on the
- The biochemical basis for the left side.
various blood types involves
monosaccharides present on
plasma membranes of red blood How are the cyclic forms of
cells (RBCs) monosaccharides drawn?
- The monosaccharides
responsible for blood groups are - In aldohexoses the OH group on
D-galactose and its derivatives C5 reacts with aldehyde carbonyl
to give two cyclic hemiacetals
called anomers. The acetal
Blood Types carbon is called anomeric
carbon. The α anomer has the
- Galactose is a component of the
OH group on the new chirality
antigen present on blood cells
center drawn down for a D, the β
that determine blood types within
anomer has the OH group drawn
ABO blood group system
up
- In A and A antigens, there are two
monomers of galactose on the
antigens
- In the B antigens there are three
monomers of galactose

KEY CONCEPTS
What are the major structural features What reduction and oxidation products
of monosaccharides? are formed from monosaccharides?

- Monosaccharides with a - Monosaccharides are reduced to

carbonyl group at C1 are called
aldoses and those with a
carbonyl at C2 are called ketoses.
Generally, all other carbons have
OH groups bonded to them. The
terms triose, tetrose and so forth
are used to indicate the number
of carbons in the chain.
- The acyclic form of
monosaccharides is drawn in
fischer projection formulas. A D
sugar has the OH group of the
alditols with H and Pd
- Monosaccharides are oxidized to
aldonic acids with Benedict’s
reagent. Sugars that are oxidized
with Benedict’s reagent are called
reducing sugars
What are the major structural features
of disaccharides?
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MODULE 8: Carbohydrates
- Disaccharides are composed of
two monosaccharides units
joined by an acetal C—O bond
called a glycosidic linkage. A α
glycoside has the glycosidic
linkage oriented down, and
βglycoside has the glycosidic
linkage oriented up
- Disaccharides are hydrolyzed to
two monosaccharides by the
cleavage of glycosidic C—O bond
with water
What are the differences in the
polysaccharides cellulose, starch and
glycogen?
- Cellulose, starch and glycogen
are all polymers of the
monosaccharides glucose
- Cellulose is unbranched polymer
composed of repeating glucose
units joined in 1→4-β- glycosidic
linkages. Cellulose forms long
chains that stack in
three-dimensional sheets. The
human digestive system does not
contain the needed enzyme to
metabolize cellulose
- There are two forms of
starch—amylase, which is an
unbranched polymer; and
amylopectin, which is a branched
polysaccharide polymer. Both
forms contain 1→4-α- glycosidic
linkages and the polymer winds
in a helical arrangement. Starch
is digestible because the human
digestive system has the needed
amylase enzyme to catalyze
hydrolysis
- Glycogen resembles amylopectin
but is more extensively branched.
Glycogen is the major form in
which polysaccharides are stored
in animals
Give examples of some carbohydrate
derivatives that contain amino groups,
amides, or carbohydrate anions
- Gylcosaminoglycans are a group
of unbranched carbohydrates
derived from amino sugar and
glucoronate units. Examples
include hyaluronate, which forms
a gel-like matrix in joints and the
vitreous humor of the eye;
chondroitin, which is a
component of cartilage and
tendons; and heparin, an
anticoagulant
- Chitin, a polymer of
N-acetyl-D-glucosamine, forms
the hard exoskeletons of carbs,
lobsters and shrimps
What role do carbohydrates play in
determining blood type?
- Human blood type—A, B, AB, O is
determined by three or four
monosaccharides attached to a
membrane protein on the surface
of red blood cells. There are three
different carbohydrates
sequences, one for each of the A,
B, and O blood types. Blood type
AB contains the sequences for
both blood type A and B. since
the blood type, blood type must
be known before receiving a
transfusion