2 - 2021-2022 Carbohydrates Chemistry Course
2 - 2021-2022 Carbohydrates Chemistry Course
2 - 2021-2022 Carbohydrates Chemistry Course
Biochemistry Department
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Learning objectives
By the end of this lecture the student should be able to
• Define Carbohydrates (CARBs)
• List functions of Carbohydrates
• Classify carbohydrates depending on number of Sugar (s)
• Describe structures of the simplest and most common
Monosaccharides
• Identify the following terms:
Isomers
Epimers
stereoisomerism
Enantiomers
Optical activity
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Define carbohydrates (CARBs)??
Carbohydrates are an organic compounds that consists of
in nature.
Note:
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Functions of carbohydrates:
1. They providing a significant fraction of the dietary calories for
most organisms. (1 gram CHO gives 4 Kcal)
2. They acting as a storage form of energy in the body (Glycogen)
3. They serving as cell membrane components that mediate some
forms of intercellular communication.
4. Carbohydrates serve as a structural component of many
organisms, including the cell walls of bacteria, the exoskeleton
of many insects, and the fibrous cellulose of plants.
5. CHO is important component of Nucleic acids
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Classification of Carbohydrates
• Monosaccharides
• Disaccharides
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• Monosaccharide Structure
Glycerol
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Monosaccharides can be classified according to:
OR
DHA
glyceraldehyde is an aldose, whereas dihydroxy acetone is a ketose
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N.B:
Glyceraldehyde:
is a triose monosaccharide with chemical
formula C3H6O3.
Dihydroxyacetone (DHA):
is a triose monosaccharide with chemical
formula C3H6O3.
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Glucose and galactose are aldoses Fructose is a
sugars ketose sugar
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Note:
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General Properties of monosaccharides Structures
Isomers
Epimers
Stereoisomerism
Enantiomers
Optical activity
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Isomers
are compounds that have the same chemical formula but have
different structures (different connectivity). For example:
Glucose, galactose mannose and fructose are all isomers of each
other , having the same chemical formula, C6H12O6
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Remember:
The carbons in sugars are numbered beginning at the end that contains the
carbonyl carbon—that is,( the aldehyde or keto group)
Epimers
Carbohydrate isomers that differ in configuration
around only one specific carbon atom
(with the exception of the carbonyl carbon)
are defined as epimers of each other.
For examples
Glucose and galactose are
C-4 epimers—their structures differ only in
the position of the –OH group at carbon 4
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Glucose and mannose are C-2 epimers.
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Enantiomers
A special type of isomerism is found in the pairs of structures that are
Non- Superposable mirror images of each other. These mirror images are called
enantiomers, and the two members of the pair are designated as a D- and an L-
sugar
Majority Of The Sugars In Humans Are D-sugars
D- isomer: -OH group on the last asymmetric carbon is on the right.
L- isomer: -OH group on the last asymmetric carbon is on the left.
Asymmetric carbon
atom
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This slide only for understanding, how many chiral
carbon are present in Glucose
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Optical activity:
The presence of asymmetric ‘C’ atom in the sugar confers
optical activity of the compound .
When a beam of polarized light is
passed through an optically active sugar
the plane of polarized light is rotated to
the Right (Dextro rotatory) or to the left (Levo rotatory).
A mixture containing equal number of D (dextrorotatory) and L
(levorotatory) molecules showing no optical activity is known as
Racemic mixture
Glucose is dextrorotatory(+),while fructose is levorotatory(-)
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Learning objectives
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Monosaccharides structure forms
Monosaccharides structures are present in two forms:
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When an alcohol adds to an aldehyde, the product is called a
hemiacetal; when an alcohol adds to a ketone the resulting product
is a hemiketal
Cyclization of monosaccharides (Ring Form)
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(Pyran and Furan)
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Anomeric carbon
• Cyclization creates an anomeric carbon (the former carbonyl carbon),
generating the α and β configurations of the sugar, for example,
• α-D-glucopyranose and β-D-glucopryanose.
• These two sugars are both glucose but are anomers of each other.
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α-D-glucopyranose β-D-glucopryanose
Fischer projection
• The carbon chain is written vertically.
• α-anomer ( α configuration): The –OH is on the acetal or ketal carbon
(anomeric carbon) projects to the same side as the ring structure formed
by the oxygen bridge (to the right).
• β-anomer(β-configuration): : -OH (on anomeric carbon) is on the
opposite side (to the left).-
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Haworth projection
The plane of the hemiacetal or hemiketal ring is flat on the paper, and the –
-OH and –CH2OH groups project either above or below the plane of
isH,a common way of representing the cyclic structure
the ring.
ofα-anomer
monosaccharides with agroup
means that the hydroxyl simple
(-OH)three-dimensional
attached to C-1 (in
perspective.
aldohexoses) or C-2 (in ketohexoses) is below the plane of the ring ( trans
to the CH2OH group, See the figure below)
β-anomer means that (-OH) is above the plane of the ring
(cis to the CH2OH group, see the figure below) .
α- form β-form
Remember
Biomedically, Glucose is the most important Monosaccharide
Straight (linear)-chain
cyclic structure
(Haworth)
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Glucose structure forms
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Which of the following statements best describes glucose?
A. It is a ketose and usually exists as a furanose ring in solution.
B. It is a C-4 epimer of galactose.
C. It is utilized in biological systems only in the L-isomeric
form.
D. It is a storage form of energy in the body.
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Learning objectives
By the end of this lecture the student should be able to
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Physical Properties of monosaccharide
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Chemical Properties of monosaccharide
1. Reducing properties (they act as reducing agents)
3. Dehydration
4. Formation of Esters
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Keep in mind
in general, Sugars are classified as
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Principles of test
• Cu+2 oxidizes the aldehyde or ketone group of the reducing sugar to form a
carboxyl group. (Glucose acts as reducing agent)
Reducing
sugar
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2. Oxidation Reduction Properties
A. Oxidation of Aldoses
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2. Oxidation of Galactose
Mucic acid (which form insoluble crystals).This test is used for the
identification of galactose.
Oxidation of most monosaccharides by nitric acid yields soluble
dicarboxylic acids. However, oxidation of galactose yields an
insoluble mucic acid.
Lactose will also yield a mucic acid, due to hydrolysis of the
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Keep in mind:
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B. Reduction
When treated with reducing agents, the
aldehyde or keto group of monosaccharides
is reduced to corresponding alcohol:
D-glucose D-sorbitol
D-galactose D-dulcitol
D-fructose D-mannitol + D-sorbitol
D-mannose D-mannitol
D- ribose D-ribitol
Note: Dextrose IV Fluid Is D- Glucose
Beause D-glucose is dextrorotatory sugar
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C. Dehydration
When treated with concentrated sulfuric acid
(H2SO4), monosaccharides undergo dehydration
with an elimination of 3 water molecules giving a
compound called furfural.
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D. Formation of Esters
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Esterification
The alcoholic groups of monosaccharide may be
esterified by non-enzymatic or enzymatic
reactions.
Esterification of carbohydrates with phosphoric
acid is a common reaction in metabolism
Glucose-6-phosphate and Glucose-1-phosphate
are good examples (ATP donates phosphate
moiety in ester formation).
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Osazone formation
Note:
Phenylhydrazine is the chemical compound
with the formula C6H5NHNH2. phenylhydrazine
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Osazone formation
General Reaction:
Osazone
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Osazone formation
Phenyl hydrazine in acetic acid, when boiled with
reducing sugars forms Osazone.
Glucose, Fructose and Mannose
Give needle shaped osazone crystal.
Disaccharides osazones
maltose give sunflower shaped
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• Osazone crystals have a characteristic shape under the light
microscope and help in the identification of the sugar type.
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Learning objectives
By the end of this lecture the student should be able to
• Identify oligosaccharides
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Derivatives of Monosaccharides
There are several derivatives of monosaccharides, some of
which are physiologically important.
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Disaccharides
The disaccharides consist of two monosaccharide (similar or
different) held together by glycosidic bond. in a dehydration
reaction
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Glycosidic bond
The bonds that link sugars are called glycosidic bonds.
They are formed by enzymes known as glycosyltransferases
that use nucleotide sugars (activated sugars) such as uridine
diphosphate glucose (UDP-G) as substrates.
Glycosidic bonds between sugars are named according to the
numbers of the connected carbons and with regard to the
position of the anomeric hydroxyl group of the first sugar
involved in the bond. If this anomeric hydroxyl is in the α
configuration, then the linkage is an α-bond. If it is in the β
configuration, then the linkage is a β-bond. 58
Maltose ( C12 H22 O11) Malt sugar
•Maltose ( C12 H22 O11) is not found in free form in the body.
•it is produced during the digestion of starch by pancreatic amylase.
• Maltose is composed of 2 α –D – Glucose units held together by ( α- 1,4 )
glycosidic bond (dehydration reaction)
Because the anomeric end of the glucose residue is not involved in the
glycosidic linkage, therefore, lactose is reducing sugar.
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Sucrose (Table sugar)
Because the anomeric end of both glucose residue and fructose residue are
involved in the glycosidic linkage, therefore, Sucrose is not reducing sugar.
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Disaccharides on hydrolysis reaction give the
following monosacharides
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Glycosidic bond Names
• If the monosaccharide is attached to OH group of another sugar, it is called
O –glycosidic linkage
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O –glycosididic bonds N –glycosididic bonds
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Complex carbohydrates
Carbohydrates can be attached by glycosidic bonds to
non-carbohydrate structures, including
• Purine and pyrimidine bases (found in nucleic acid)
• aromatic rings (such as those found in steroids and
bilirubin (They are made more soluble by conjugation
with glucuronic acid during their metabolism)
• glycoproteins and proteoglycans)
• Lipids (found in glycolipids).
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Oligosaccharides
Chen, Liyan. (2013). Value added products from soybean: removal of anti-nutritional factors via bioprocessing.
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All of the following sugars are reducing Sugars
Except
a. Glucose
b. Maltose
c. Fructose
d. Sucrose
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Learning objectives
By the end of this lecture the student should be able to
• Define polysaccharides and their functions
• Classify polysaccharides
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Polysaccharide
polysaccharides are hydrolysable polymers of
more than 10 sugar units. They consist of
monosaccharides held together by glycosidic bonds.
Function of Polysaccharide
Structural and Storage of energy
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Polysaccharides are classified into :
Homo polysaccharides:
Are Polymers Of a single Monosaccharide.
Examples : Starch, Glycogen.
Hetero polysaccharides:
Are polymers of different monosaccharides.
e. g (Glycosaminoglycans).
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Homo Polysaccharide
Homopolysaccharides exist as branched and
unbranched polymers
Unbranched
Branched
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Starch (Homopolysaccharide)
• Structure:
• Starch is a homopolysacharide composed of D-glucose units held together
by α-glycosidic bonds. It is known as glucosan or glucan.
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Starch is Composed of two types of polymers:
Amylose: linear chain of glucose units
Amylopectin: branched chain of glucose units
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Glycogen (Homopolysaccharides)
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Function of Glycogn
The storage form of glucose
Muscle glycogen
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Amounts of liver and muscle glycogen
Approximately 400 g of glycogen make up
1–2% of the fresh weight of resting muscle
Approximately 100 g of glycogen make up to
10% of the fresh weight of a well-fed adult liver.
Note: In the body, muscle mass is greater than
liver mass. Consequently, most of the body’s
glycogen is found in muscle.
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Fluctuation of glycogen stores
Liver glycogen stores increase during the well-fed state
, and are depleted during fasting.
Muscle glycogen is not affected by short periods of
fasting (a few days) and is only moderately decreased in
prolonged fasting (weeks).
Muscle glycogen is synthesized to replenish muscle
stores after they have been depleted following strenuous
exercise.
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Structure of glycogen
Glycogen is a branched-chain polysaccharide made exclusively from α-D-glucose.
The primary glycosidic bond is an α (1→4) linkage.
After an average of eight to ten glucosyl residues, there is a branch containing
an α (1→6) linkage. These molecules exist in discrete cytoplasmic granules that also
contain most of the enzymes necessary for glycogen synthesis and degradation.
α1,6-glycosidic
bond
α1,4-glycosidic bond 78
Glycogen and amylopectin differ only by the interval in which
the branch point are inserted in the polymer: both are polymers of
α1,4-glucose unit with α1,6-glucose branches;
glycogen branches every 8-10 glucosyl residues, whereas
amylopectin branches every 24-30 glucosly residues.
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Cellulose (Homopolysaccharides)
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Summary Of HomoPolysaccharides types and
related glycosidic bonds
α (1-4) glycosidic
linkage
α (1-4) glycosidic
linkage
α (1-6) glycosidic
linkage
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Learning objectives
By the end of this lecture the student should be able to
• Define heteropolysaccharides and their functions
• Classify GAGs
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Hetro Polysaccharide:
They are the polysaccharides which composed
of different types of sugars.
2 monomer type
Unbranched
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Glycosaminoglycans (GAGs) Structure
associated with
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Glycosaminoglycans (GAGs) Structure
GAGs are long, unbranched, heteropolysaccharide composed of
repeating disaccharide chains where one of the sugars is
an N-acetylated amino sugar and the other is an acidic sugar.
(Fig. 14.1)
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The amino sugar
is either D-glucosamine or
D-galactosamine in which the amino
group is usually acetylated eliminating its
positive charge.
{(N-acetylglucosamine (GlcNAc) or N-
acetylgalactosamine (GalNAc)} , The
acidic sugar
is either D-glucuronic acid or its C-5
epimer, L-iduronic acid. These uronic
sugars contain carboxyl groups that are
negatively charged at physiologic pH and,
together with the sulfate groups, give
GAGs their strongly negative nature.
(Figure 14.2).
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.
Glycosaminoglycans (GAGs) Properties
producing the gel-like matrix that forms the basis of the body’s ground
• Hydrated GAGs serve as a flexible support for the ECM, interacting with
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glycoprotein
GAG
GAG
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The glycosaminoglycans are divided into
six major classes:
Hyaluronic acid
Chondroitin 4-and 6 sulfate
Keratan sulfate
Dramatan sulfate
Heparin
Heparan sulfate 91
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The differences between glycoprotein and Proteoglycan
Glycoproteins Proteoglycans
Structure ★ Oligosaccharide ★ Glycosaminoglycan (GAG) chain(s) are
(carbohydrate) chains are attached to a polypeptide side chain.
covalently attached to a
polypeptide side chain.
Nature of Chains ★ Oligosaccharide chains are ★ Glycosaminoglycan chains are long,
short, branched, and may or may linearized, and negatively charged because of
not be negatively charged. the presence of sulfate and uronic acid
functional groups.
Non-protein ★ 10 - 15% by weight 50 - 60% by weight
Content
Subtypes ★ Broadly categorized as N- ★ Classification depends on the nature of the
linked and O-linked saccharides. GAG chains.
Location ★ Glycoproteins are found on ★ Proteoglycans are found in the connective
the cell surface with the tissues
carbohydrate chains placed
outside the cell.
Function ★ Glycoproteins act as integral ★ Proteoglycans provide structural support
membrane proteins, and play a and mechanical strength to the ECM, play a
role in cell-cell recognition and role in the modulation of cell growth
signaling. processes, and provide padding in joints.
★ Thrombospondin ★ Aggrecan
★ Chondronectin ★ Perlecan
★ ABO blood group antigens ★ Neurocan 93
★ Hormones like follicle ★ Syndecan
All of the following are false Except
a. Glycogen is a branched chain of glucose polymers
b. Starch contains amino sugar
c. GAGs contain large amount of proteins
d. Hyaluronic acid contains sulfate group
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