Carbohydrates

Carbohydrates
• Carbohydrate: polyhydroxy aldehydes or
ketones or compounds that produce such
substances upon hydrolysis

CHO CH2OH
H OH
Aldehyde O Ketone
HO H HO H
H OH H OH
H OH H OH
CH2OH
Polyhydroxy
CH2OH
Polyhydroxy ketone
aldehyde Glucose Fructose

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 Functions of Carbohydrates in the Human
Body
• Major source of energy
• Carbohydrate storage, in the form of glycogen, provides a
short-term energy reserve
• Carbohydrates supply carbon atoms for the synthesis of other
biochemical substances (proteins, lipids, and nucleic acids)
• Carbohydrates form part of the structural framework of DNA
and RNA molecules
• Carbohydrates linked to lipids are structural components of
cell membranes
• Carbohydrates linked to proteins function in a variety of cell–
cell and cell–molecule recognition processes

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• Monosaccharide: a carbohydrate that cannot
be hydrolyzed to a simpler carbohydrate
• Building blocks of all carbohydrates
– They have the general formula CnH2nOn or
Cn(H2O)n (hydrates of C) , where n is the number of
atoms

• Aldose: a monosaccharide containing an aldehyde

group
• Ketose: a monosaccharide containing a ketone
group
• Trioses are simplest carbohydrate monosaccharides
Examples of monosaccharides found in humans, classified
according to the number of carbons they contain.
 MONOSACCHARIDES OF BIOLOGICAL
SIGNIFICANCE
MONOSACCHARIDE ALDOSES KETOSES
Trioses (C3H6O3) Glycerose Dihydroxyacetone
(glyceraldehyde)

Tetroses (C4H8O4) Erythrose Erythrulose

Pentoses (C5H10O5) Ribose, Arabinose, Ribulose, Xylulose

Xylose

Hexoses (C6H12O6) Glucose, Galactose. Fructose

Mannose

Heptoses (C7H14O7) --------------- Sedoheptulose

07/22/2024 Biochemistry For Medics- Lecture notes 8

 DISACCHARIDES OF BIOLOGICAL
SIGNIFICANCE
Sugar Composition Source
Isomaltose O-α-D-glucopyranosyl- Enzymic hydrolysis of
(1->6)-α-D-glucopyranose starch (the branch points in
amylopectin)
Maltose O-α-D-glucopyranosyl- Enzymic hydrolysis of
(1->4)-α-D-glucopyranose starch (amylase);
germinating cereals and
malt

Lactose O-α-D-galactopyranosyl- Milk (and many

(1->4)-β-D-glucopyranose pharmaceutical
preparations as a filler)
Sucrose O-α-D-glucopyranosyl- Cane and beet sugar,
(1->2)-β-D- sorghum and some fruits
fructofuranoside and vegetables

07/22/2024 Biochemistry For Medics- Lecture notes 9

Aldoses
Ketoses
 Stereoisomers
• Stereoisomers are isomers that have the same
molecular and structural formulas but differ in
the orientation of atoms in space.
• Two types:
• Enantiomers are stereoisomers whose
molecules are nonsuperimposable mirror images
of each other. Molecules with chiral center.
• Diastereomers are stereoisomers whose
molecules are not mirror images of each other.

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Stereoisomers of Aldotetroses
Stereoisomers
 Fischer Projections
• Fischer projection: bonds are
written in a two dimensional
representation showing the
configuration of tetrahedral
stereocenters
• horizontal lines represent
bonds projecting forward
(Wedge)
• vertical lines represent
bonds projecting to the rear
(Dash)
• the carbon atom at the
intersection of the
horizontal and vertical lines
is not shown
 Objects and Mirror Images
• Most monosaccharides exist in two forms: a
“left handed” and “right handed” form - same
as two hands

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 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
 D,L Monosaccharides
– The most common D-tetroses and D-pentoses are:
CHO CHO
CHO CHO H OH H H
H OH HO H H OH H OH
H OH H OH H OH H OH
CH2 OH CH2 OH CH2 OH CH2 OH
D-Erythrose D-Threose D-Ribose 2-Deoxy-D-ribose

– The three most common D-hexoses are:

CHO CHO CH2 OH
H OH H OH C= O
HO H HO H HO H
H OH HO H H OH
H OH H OH H OH
CH2 OH CH2 OH CH2 OH
D-Glucose D-Galactose D-Fructose
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
 Haworth Projections
• Haworth projections
– five- and six-membered hemiacetals are
represented as planar pentagons or hexagons, as
the case may be, viewed through the edge
– most commonly written with the anomeric carbon
on the right and the hemiacetal oxygen to the
back right
– the designation -means that -OH on the
anomeric carbon is cis to the terminal -CH2OH; -
means that it is trans
 Haworth Projections (Cont’d)
• A six-membered hemiacetal ring is shown by the
infix -pyran- (pyranose)
• A five-membered hemiacetal ring is shown by the
infix -furan- (furanose)
• Five-membered rings are so close 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
 Haworth Projections
• In the terminology of carbohydrate chemistry,
– b means that the -OH on the anomeric carbon is
on the same side of the ring as the terminal -
CH2OH.
“Beta get up for breakfast”
– a means that the -OH on the anomeric carbon is
on the side of the ring opposite from the terminal
-CH2OH.
– A six-membered hemiacetal ring is called a
pyranose, and a five-membered hemiacetal ring
is called a furanose.
O O
Fura n Pyran
Haworth Projections (Cont’d)
Comparison of the Fischer and
Haworth Representations
 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 ketones react with alcohols to
form hemiacetals.
– Cyclic hemiacetals form readily when the hydroxyl
and carbonyl groups are part of the same
molecule and their interaction can form a five- or
six-membered ring.
O redraw to show
1 -OH and -CHO
4
H close to each other
O-H
4-Hydroxypentanal 1
H H
4
C
O O O O-H
H A cyclic hemiacetal
 Cyclic Structure
• Monosaccharides have -OH and C=O groups in
the same molecule and exist almost entirely as
five- and six-membered cyclic hemiacetals
• anomeric carbon: the new stereocenter resulting
from cyclic hemiacetal formation
• anomers: carbohydrates that differ in
configuration only at their anomeric carbons
Formation of a Cyclic Hemiacetal
 Cyclic Hemiacetal
Exhibits Mutarotation
 interconversion between the α and β anomers
 they can exists in α OR β form

Glucose is blood sugar

 Cyclic Hemiketal
Exhibits Mutarotation
 interconversion between the α and β anomers
 they can exists in α OR β form
 Chair Conformations
• For pyranoses, the six-membered ring is more
accurately represented as a chair
conformation.
anomeric
carbon
CH2 OH
HO O
HO
OH()
OH
 -D-Glucopyranose
( - D-Glucose)

CH2 OH CH2 OH
HO OH HO O
HO O HO
C
OH H
HO
OH( )
D-Glucose
- D-Glucopyranose
(  - D-Glucose)
 Chair Conformations
– In both Haworth projections and chair
conformations, the orientations of groups on
carbons 1- 5 of b-D-glucopyranose are up, down,
up, down, and up.
6
CH2 OH
6
5
H O OH() 4 CH2 OH
H HO O
4 OH 1
H HO 5
HO H 2 OH( )
3
3 2 OH 1
H OH
-D-Glucopyranose  - D-Glucopyranose
(Haworth projection) (chair conformation)
 Chair is the most STABLE
conformation.
Hydrogens are axial and larger
substituents are equatorial – less
opportunity for steric interactions.
 Reaction of Monosaccharides
• Reducing sugar: one that reduces an oxidizing agent
Sugars that can be oxidized are called reducing sugars
• Oxidation of a cyclic hemiacetal form gives a lactone
• When the oxidizing agent is Tollens solution, silver
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
Aldehydes when oxidized form an acid (carboxylic acid)
 Glucose

D- Glucose D- Gluconic Acid

 Reduction of Monosaccharides
• Monosaccharides can be reduced turning the
carbonyl group into an alcohol group.
• The resultant product is a sugar alcohol.
• The products named by replacing the -ose
ending with -itol.
• Glucose forms sorbitol (glucitol).
• Mannose forms mannitol.
• Fructose forms a mixture of mannitol and
sorbitol.
• Glyceraldehyde forms glycerol.
Glycoside is a molecule in which a sugar is bound to another
functional group via a glycosidic bond.
 Important derivatives of monosaccharides
Amino sugars
They are formed by replacing the hydroxyl group (at C2 usually)
of monosaccharides by amino group.
The most common amino sugars are glucosamine and
galactosamine.
-Glucosamine is present in Heparin, Hyaluronic acid and blood
group substances.
-Galactosamine is present in Chondroitin of cartilages and
tendons.
 Disaccharides
• A disaccharide is formed when the hemiacetal or
hemiketal group on one monosaccharide reacts
with one of the hydroxyl groups on another
monosaccharide with the elimination of water.
• Two monosaccharides combined together by
glycosidic linkage.

– The acetal or ketal formed is called a glycoside.

– The C-O-C bond is called a glycosidic bond.

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Reducing Disaccharides
• Maltose: 2 α-D-glucose units held together by
α(1→4) glycosidic bond.

• Lactose: β-D-galactose & β-D-glucose units

held together by β(1→4) glycosidic bond

• Cellobiose: Two β-D-glucose units held

together by β(1→4) glycosidic bond.
 Non-reducing Disaccharides
• Sucrose: α-D-glucose & β-D-fructose units held
together by (α1→β2) glycosidic bond. (an invert
sugar when hydrolyzed)

• Trehalose: Two α-D-glucose units held together

by (α1→ α1) glycosidic bond.
 CONCEPT REVIEW
What monosaccharides are obtained by the
hydrolysis of each disaccharide?
A. Sucrose
D-glucose and D-fructose
B. Maltose
two molecules of D-glucose
C. Lactose
D-glucose and D-galactose
Polysaccharide
• Repeat units of monosaccharides or their
derivatives held together by glycosidic bonds.
• Two main functions:
- Energy Storage
- Structure
• Can either be Homopolysaccharide or
Heteropolysaccharide
Polysaccharide
Homopolysaccharide
Starch: Consists of
Amylose (water soluble) &
Amylopectin (water
insoluble).
Amylose - 200 –20,000 D-
glucose units held
together by α(1→4)
glycosidic linkages.
Amylopectin: Branched
chain. α(1→6) glycosidic
bonds at branches) ; 20 –
30 glucose units per
branch.
Homopolysaccharide
• Glycogen: Reserve
carbohydrate in
animals.
• Stored in liver & muscle.
• Contains primer
protein: Glycogenin.
• More branched than
amylopectin linked by
α(1→4) and α(1→6).
Homopolysaccharide
• Cellulose:
• Chief carbohydrate in plants
• Made up of repeating units
of cellubiose
• Cannot be digested by
humans
Homopolysaccharide
Inulin – repeating β-D-fructose units linked by
β(1→2)
- acts as a marker for glomerular filtration
since it is not synthesized, metabolized
but filtered completely by glomerulus.

Chitin – abundantly found in crustaceans

eg.lobsters,crabs,shrimps,insects.
- Composed of N-acetyl glucosamine units
joined by β-1,4 glycosidic linkages.
Mucopolysaccharides
• Also known as GLYCOSAMINOGLYCANS (GAGs)
• Most abundant heteropolysaccharides in the body.
• These molecules are long unbranched polysaccharides
containing a repeating disaccharide unit.
• The repeating unit (except for keratan) consists of an amino
sugar (N-acetylglucosamine or N-acetylgalactosamine) along
with a uronic sugar (glucuronic acid or iduronic acid) or
galactose.
• GAGs are highly polar and attract water. They are therefore
useful to the body as a lubricant or as a shock absorber.
Mucopolysaccharides
1. Hyaluronic acid - Present in connective tissues,
tendons, synovial fluid and vitreous humor
2. Heparin - Anticoagulant. Bind and activate
Antithrombin III, which in turn activates Thrombin,
Factor X & Factor IX
3. Chondroitin sulfate - Present in ground substances
of connective tissues of cartilages, bones & tendons
4. Keratan sulfate – the only GAG without a Uronic acid
unit, found in the cornea
5. Dermatan sulfate – found in skin, blood vessels and
heart vessels
Mucopolysaccharides
Blood Types and Monosaccharides
• Blood Types and Monosaccharides: Human
blood is classified into four types: A, B, AB,
and O.
• The biochemical basis for the various blood
types involves monosaccharides present on
plasma membranes of red blood cells.
• The monosaccharides responsible for blood
groups are D-galactose and its derivatives.

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 Blood Types
• Galactose is a component of the antigens
present on blood cells that determine blood
type within the ABO blood group system.
• In O and A antigens, there are two
monomers of galactose on the antigens
• In the B antigens there are three monomers
of galactose.

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