Carbohydrates

Classification of Polysaccharides
 Homoglycans
 Heteroglycans

Polysaccharides are also called as glycans.

-made up of large number of monosaccharides linked by glycosidic linkages.

 Smaller glycans are called as oligosaccharides (10-15 monomers) found attached to

popypeptides in glycoproteins and some glycolipids.

-found in membrane and secretary proteins.

Homoglycans
-found in starch, glycogen, cellulose and chitin.
Starch, glycogen, cellulose give D-glucose when hydrolysed.
 Starch –energy storage molecule in plants.
 Glycogen –energy storage molecule in animals.
 Chitin – component of exoskeleton of insects, cell wall of fungi, yields glucose derivative N-
acetylglucosamine when hydrolyzed.

Starch (Storage Polysaccharides)

Significant source of carbohydrate in human diet.
Source- potatoes, rice, wheat, corn.

Amylose
Composed of long, unbranched chains of S-glucose residues that are linked by a(1,4) glycosidic bonds.
 Have one reducing end in which the ring can open to form free aldehyde group with reducing
properties.
 Contains several thousand glucose residues has molecular weight 150,000 to 600,000.
 Linear amylose molecule forms tight helices.
 Gives blue colour with iodine due to interaction between iodine molecules and the helically
arranged glucose rsidues.

Amylopectin
is branched polymer containing a(1,4) and a(1,6)glycosidic linkages.
 The a(1,6) points may occur every 20 to 35 residues and prevent helix formation.
 Starch digestion begins in the mouth where the salivary enzyme a- amylase initiates hydrolysis
of glycosidic bonds.
 Digestion continues in the small intestine where pancreatic a-amylase hydrolyzes all the a(1,4)
glycosidic bonds except the branch points.
 The products of a- amylase maltose, trisaccharide maltotriose and a limit dextrin.
 Starch - Structure

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Glycogen (Storage Polysaccharides)
-Storage carbohydrate in vertebrates.
-Found in liver and skeletal muscle.
 Structure similar to amylopectin except that it has more branch point possibly at every fourth
glucose residue.

Structure of Glycogen

Cellulose (Structural Polysaccharides)

Polymer of D-glucopyranose residues linked by b(1,4) glycosidic bonds. Unbranched
Structural polysaccharide in plants.
Pairs of unbranched cellulose molecules may contain as many as 12,000 glucose units each held
together by hydrogen bonding to form sheet like strips called microfibrils. These structures are found in
primary and secondary cell walls of plants.

 The ability to digest cellulose is found in microorganism which contain the enzyme cellulase.

Cellulose can be hydrolyzed to its constituent glucose units by microorganisms that inhabit the digestive
tract of termites and ruminants.
Cellulose makes up dietary fiber.
Paper, wood, textiles are some of cellulose containing products.

Chitin (Structural Polysaccharide)

Chitin is an unbranched polymer of N-Acetyl-D-glucosamine.
It is found in fungi and is the principal component of arthropod and lower animal exoskeletons, e.g.,
insect, crab, and shrimp shells.
It may be regarded as a derivative of cellulose, in which the hydroxyl groups of the second carbon of
each glucose unit have been replaced with acetamido (-NH(C=O)CH3) groups.

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Heteroglycans
High molecular weight carbohydrate polymers that contain more than one kind of monosaccharides.
Major classes found in animals are N and O-linked glycans attached to proteins.

Glycosaminoglycans (GAGs)
Glycosaminoglycans (GAGs) are large complexes of negatively charged heteropolysaccharide chains.
They are generally associated with a small amount of protein, forming proteoglycans, which typically
consist of over 95% carbohydrate.

Glycosaminoglycans have the special ability to bind large amounts of water, thereby producing the gel-
like matrix that forms the basis of the body's ground substance, which, along with fibrous components
such as collagen, make up the extracellular matrix.

The viscous, lubricating properties of mucous secretions also result from the presence of
glycosaminoglycans, which led to the original naming of these compounds as mucopolysaccharides.

Structure of Glycosaminoglycans
Glycosaminoglycans are long, unbranched, heteropolysaccharide chains generally composed of a
repeating disaccharide unit [acidic sugar–amino sugar] n.

The amino sugar is either D-glucosamine or D-galactosamine, in which the amino group is usually
acetylated, thus eliminating its positive charge.
The amino sugar may also be sulfated on carbon 4 or 6 or on a nonacetylated nitrogen.
The acidic sugar is either D-glucuronic acid or its carbon-5 epimer, L-iduronic acid.

A single exception is keratan sulfate, in which galactose rather than an acidic sugar is present.
These acidic sugars contain carboxyl groups that are negatively charged at physiologic pH and, together
with the sulfate groups, give glycosaminoglycans their strongly negative nature.
Some monosaccharide units found in glycosaminoglycans.

Functions of GAGs
Because of their large number of negative charges, these heteropolysaccharide chains tend to be
extended in solution.
 They repel each other, and are surrounded by a shell of water molecules.
 When brought together, they “slip” past each other, much as two magnets with the same
polarity seem to slip past each other.
 This produces the “slippery” consistency of mucous secretions and synovial fluid.
 When a solution of glycosaminoglycans is compressed, the water is “squeezed out” and the
glycosaminoglycans are forced to occupy a smaller volume.
 When the compression is released, the glycosaminoglycans spring back to their original,
hydrated volume because of the repulsion of their negative charges.
 This property contributes to the resilience of synovial fluid and the vitreous humor of the eye.

Classification of the glycosaminoglycans

The six major classes of glycosaminoglycans are divided according to monomeric composition, type of
glycosidic linkages, and degree and location of sulfate units.

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Structure and distribution of glycosaminoglycans (GAGs)

Hyaluronic Acid
Hyaluronate molecules may consist of as many as 25,000 disaccharide units, with molecular
weights of up to 107.
Hyaluronates are important components of the vitreous humor in the eye and of synovial fluid,
the lubricant fluid of joints in the body.
The chondroitins and keratan sulfate are found in tendons, cartilage, and other connective
tissue, whereas dermatan sulfate, as its name implies, is a component of the extracellular matrix
of skin.

 Heparin, with the highest net negative charge of the disaccharides shown, is a natural
anticoagulant substance.

Proteoglycans
High carbohydrate content (about 95%).
Occur on cell surfaces or are secreted into extracellular matrix.

Structure of proteoglycans
All of the glycosaminoglycans, except hyaluronic acid, are found covalently attached to protein,
forming proteoglycan monomers.

A proteoglycan monomer found in cartilage consists of a core protein to which the linear
glycosaminoglycan chains are covalently attached.

These chains, which may each be composed of more than 100 monosaccharides, extend out
from the core protein, and remain separated from each other because of charge repulsion.

The resulting structure resembles a “bottle brush”. In cartilage proteoglycan, the species of
glycosaminoglycans include chondroitin sulfate and keratan sulfate.

A proteoglycan monomer found in cartilage consists of a core protein to which the linear
glycosaminoglycan chains are covalently attached.

Linkage region of glycosamino-glycans

Linkage between the carbohydrate chain and the protein: This linkage is most commonly through a
trihexoside (galactose-galactose-xylose) and a serine residue, respectively.

An O-glycosidic bond is formed between the xylose and the hydroxyl group of the serine.

Proteoglycan aggregates
The proteoglycan monomers associate with a molecule of hyaluronic acid to form proteoglycan
aggregates. The association is not covalent, but occurs primarily through ionic interactions between the
core protein and the hyaluronic acid. The association is stabilized by additional small proteins called link
proteins .

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Examples of proteoglycans
 Syndecans
 Glycipcans
 Aaffrecans

The syndecans are a class of heparan sulfate and chondroitin sulfate containing proteoglycans in which
the core protein is a transmembrane protein.

Aggregans are found in cartilage.

Mucopolysaccharidoses
The mucopolysaccharidoses are hereditary disorders (1:25,000 births) that are clinically progressive.
They are characterized by accumulation of glycosaminoglycans in various tissues, causing varied
symptoms, such as skeletal and extracellular matrix deformities, and mental retardation.

Mucopolysaccharidoses are caused by a deficiency of any one of the lysosomal hydrolases normally
involved in the degradation of heparan sulfate and/or dermatan sulfate .

Functions of Proteoglycans
 Organizing extracellular matrix.
 Membrane bound syndecans, glycipcans bind to specific signal molecules like growth factors
involved in cell cycle regulation.
 Because of their vast number of polyionic GAG chains, the aggrecans trap large volume of water.
 Give strength, flexibility to cartilage and tensile strength to collagen fibers.

Glycoproteins
Proteins that are linked covalantly to carbohydrates through N- or 0- linkages.
Carbohydrate content varies from 1% to more than 85% of total weight.
Carbohydrates include monosaccharides or disaccharides such as those attached to collagen or
branched oligosaccharides found on plasma glycoproteins.

Functions of glycoproteins
 Membrane-bound glycoproteins participate in a broad range of cellular phenomena, including
cell surface recognition (by other cells, hormones (insulin receptors), and viruses),
 cell surface antigenicity (such as the blood group antigens),
 as components of the extracellular matrix and
 of the mucins of the gastrointestinal and urogenital tracts, where they act as protective biologic
lubricants.
 Sialic acid residues are responsible for high viscosity and luricating properties of saliva.
 Cellular adhesion eg selectins (transient cell-cell interaction), intergins (cell attachment to
components of extracellular matrix) and cadherins (calcium dependent binding of cells to each
other within tissue.

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Differences between Glycoproteins and Protoglycans

They differ from the proteoglycans (which might be considered a special case of glycoproteins) in that
the length of the glycoprotein's carbohydrate chain is relatively short (usually 2–10 sugar residues in
length, although they can be longer).

In addition, whereas glycosaminoglycans have diglucosyl repeat units, the carbohydrates of

glycoproteins do not have serial repeats.

The glycoprotein carbohydrate chains are often branched instead of linear, and may or may not be
negatively charged.

Glycoproteins contain highly variable amounts of carbohydrate.

For example, immunoglobulin IgG, contains less than 4% of its mass as carbohydrate, whereas human
gastric glycoprotein (mucin) contains more than 80% carbohydrate.

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Questions:

 What are disaccharides and how can the linkage occur?

 Two monosaccharides linked by a glycosidic bond
 Linkages can occur between the anomeric carbon of one sugar and a hydroxyl on another sugar

 What are the name of linkages in disaccharides based on and in what form are sugars abosorbed in
the body?
 Linkages are named based on the number of the carbon atoms involved
 In the body, sugars are absorbed as monosaccharides and digestion requires specific enzymes
(e.g., lactase)

 What are the key disaccharides?

 Lactose
 Maltose
 Cellabiose
 Sucrose

 What is lactose, how is it formed, and what is its linkage?

 A disaccharide found in milk.
 A combination of galactose and glucose.
 Beta(1,4) linkage.
 Requires lactase to digest (expression decreases following childhood).

 What is maltose, how is it formed, and what is its linkage?

 A disaccharide that is the intermediate product of starch hydrolysis
 Alpha (1,4) linkage between two D-glucose molecules
 Does not appear freely in nature
 In solution the free anomeric carbon undergoes mutarotation

 What is cellobiose, how is it formed, and what is its linkage?

 A disaccharide that is the degradation product of cellulose
 Contains two D-glucose molecules with a beta (1,4) linkage
 Does not occur freely in nature.

 What is sucrose, how is it formed, and what is its linkage?

 A disaccharide: table sugar (cane or beet sugar)
 Formed from alpha-glucose and beta-fructose
 alpha, beta (1,2) linkage
 Produced in the leaves and stems of plants
 Non-reducing sugar

 What are polysaccharides?

 Also called glycans
 Composed of a large number of monosaccharides connected by glycosidic linkages

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 What are oligosaccharides?
 Smaller glycans with up to 10-15 monomers
 Most often attached to polypeptides in glycoproteins and some glycolipids.

 What are the two classes of polysaccharides?

 Homoglycans
 Heteroglycans

 What are homoglycans?

Polysaccharides composed of a single type of monosaccharide

 What are heteroglycans?

Polysaccharides composed of two or more different types of monosaccharides.

 What are the most abundant homoglycans found in nature and what are they made of?
Starch, glycogen, and cellulose are all made from D-glucose
Chitin is made of N-acetylglucosamine

 What is the molecular weight polysaccharides?

Polysaccharides like starch and glycogen have no fixed molecular weight, unlike proteins and nucleic
acids. This means there is not necessarily a limit as to how many monomers can be combined
In a “well fed” state, the liver synthesizes glycogen until the blood sugar levels reach proper levels

 What is starch?
Energy reservoir in plant cells and a significant energy (carbohydrate) source in the human diet (e.g.,
potatoes, rice, corn, wheat)
A homoglycan

 What are the two different polysaccharides that form starch?

Amylose and Amylopectin

 What is amylopectin, how is it formed, and digested?

One of the polysaccharides that form starch
Made of branched chains of D-glucose with alpha(1,4) and alpha(1,6) linkages
Digestion involves amylase in the mouth and small intestine, followed by other enzymes designed to
release the glucose monomers

 What is amylose, how is it formed, and what is its useful function?

One of the polysaccharides that form starch
Made of unbranched chains of D-glucose with alpha (1,4) linkages
Ideal for storage

 What are glycogens and where are they most abundant?

A homoglycan
Carbohydrate storage form used by vertebrates
Most abundant in liver and muscle cells

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 Describe the sturcture of glycogen
Involves a compact branched chains of D-glucose similar to the structure of amylopectin
The numerous non-reducing ends allows the cell to rapidly break glycogen down and release glucose

 Describe the similarities of linkages in gylcogen and amylopectin

These polysaccharides have both alpha(1,4) [for the chain] and alpha(1,6) [for thebranches] linkages

 What is cellulose, where is it most abundant?

A homoglycan and structural polysaccharide in plants
Probably the most abundant organic substance on earth
Considered a good dietary fiber for animals

 Describe the formation, structure, and linkage of cellulose

Made of D-glucopyranose
Beta (1,4) linkages
Unbranched chains pair together via H-bonds (microfibril)
40 pairs combine to form a bundle, which is the structural form found in plant cells

 What are 5 types of heteroglycans?

N-glycans
O-glycans
Glycosaminoglycans (GAGs)
Glycan components of glycolipids
GPI anchors (glycosylphosphatidylinositol)

 What are N-glycans, how are they formed, and what is its linkage?
A heteroglycan
Sugar groups linked to the nitrogen of the side chain amide of an asparagine residue
Involves a beta-glycosidic bond between nitrogen and the anomeric carbon of N-acetylglucosamine
Involves several different monosaccharides

 What are O-glycans, how are they formed, and what is its linkage?
Core of galactosyl-b-(1,3)-N-acetylgalactosamine linked to the protein with an a-glycosidic bond to
the oxygen of the side chain of serine or threonine residues
Collagens have a similar linkage with hydroxylysine using a different core
Several other kinds sugars are attached to the core

 What are glycosaminoglycans (GAGs) and what does it generally contain?

A heteroglycan
Linear polymers of repeating dissacharides
Generally contain a 6-carbon uronic acid (CH2OH to carboxylic acid)

 What does the repeating groups of Glycosaminoglycans (GAGs) contain and what are its features?
Repeating groups contain both carboxyl and sulfate groups (negative charges!)
Charge repulsion keeps chains separated and the hydrophilicity attracts and maintains large volumes of
water – vastly increasing the volume of space occupied

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 What are the five classes of glycosaminoglycans (GAGs) and how are they connected to proteins?
hyaluronic acid, chondroitin sulfate, dermatan sulfate, heparin and heparan sulfate, and keratan sulfate
All are connected to protein via serine or threonine except hyaluronic acid which connects via
asparagine

 What is chondroitan sulfate?

A heteroglycan (GAG)
Component of cartilage

 What is dermatan sulfate?

A heteroglycan (GAG)
Found primarily in skin

 What is Heparin?
A heteroglycan (GAG)
Anticoagulant, found in mast cells
Heparan very similar but has fewer sulfate and more acetyl groups

 What is keratan sulfate?

A heteroglycan (GAG)
Found in cornea, cartilage, and intervertebral disks

 What is hyaluronic acid?

A heteroglycan (GAG)
Found in the vitreous humor of the eye and synovial fluid of joints

 What are glycoconjugates?

Compounds that covalently bind carbohydrates with either lipids or proteins
Serve structural and functional roles generally on the surface of cells or in the extracellular matrix

 What are the classes of glycoconjugates?

Glycolipids
Proteoglycans
Glycoproteins

 What is the difference between proteoglycans and glycoproteins

Proteoglycans have a higher carbohydrate content
Glycoproteins do not usually have uronic acids, sulfate groups, and disulfide repeating groups (GAGs)

 Where are proteoglycans present?

Present on the cell surface or secreted into the extracellular matrix
 How are proteoglycans formed and what is its structure?
Made of GAGs linked to proteins (called core proteins) using N- and O-glycosidic linkages
Proteoglycan aggregates are a series of proteoglycans linked to a common central GAG backbone
(hyaluronic acid)

 What are 3 examples of proteoglycans?

Syndecans

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Glypicans
Aggrecan

 What are syndecans?

A class of heparan sulfate and chondrotin sulfate containing proteoglycans which include a
transmembrane core protein
 What are Glypicans?
Are proteoglycans that contain heparan sulfate and are linked to membranes via GPI anchors
 What are aggrecans?
Proteoglycans found in cartilage
Combination of chondroitin sulfate and keratan sulfate attached to a core

 What are the functions of proteoglycans?

Signaling and Structural (compressive stiffness)
 What is the backbone of a proteoglycan aggregate?
Hyaluronic acid (GAG) backbone
 What are glycoproteins and how are they linked?
Glycoconjugates
Proteins that are linked through N- or O-linkages to carbohydrates (i.e., N- or O-glycans)

 What is the range of carbohydrate content in glycoproteins?

Carbohydrate content ranges from ~1-85%
Carbohydrates involved include monosaccharides, disaccharides, and several types of oligosaccharides

 How are the N and O linkages formed in gylcoproteins?

N-linked carbohydrate chains are formed initially and then added to the protein during synthesis
(carbohydrate added on protein)
O-linked chains are built directly on the protein in the Golgi (carbohydrate built on protein)

 What are 5 examples of glycoproteins?

Immunoglobulin (antibodies)
Hormones: chorionic gonadotropin (HCG), follicle-stimulating hormone (FSH)
Metal transport proteins: transferrin and ceruloplasmin
Membrane protein such as Na+-K+-ATPase (Na+-K+pump)
ABO blood group system- most common example

 What is the glycocalyx?

Layer outside of most eukaryotic cells containing a large number of carbohydrates
These serve structural, signaling, and recognition roles for cells and tissues
Glycoproteins are components of the glycocalyx

 What are lectins?

Considered to be the translators of the sugar code.
Carbohydrate-binding proteins that are not abs and have no enzymatic activity.

 How does the cell recognize the vast array of different carbohydrates?
Proteins known as lectins are able to bind to specific carbohydrate groups
These are used in numerous types of interactions for recognition – especially cell-cell (e.g., selectins)

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 What is glycolysis?
Break down of glucose to produce energy

 What is gluconeogenesis?
Production of glucose from specific precursors

 What is pentose phosphate?

Involved in the production of ribose for nucleotides

 What is considered glycogen metabolism?

The building (glycogenesis) or breakdown (glycogenolysis) of glucose

 What daily value percentage is considered low and high of total carbohydrates?
5% or less is Low
20% or more is High

 What are the dietary sources of carbohydrates?

Sugar
Starch- complex carbohydrate
Dietary fiber- complex carbohydrate

Where is sugar found?

In a range of food sources such as milk (lactose), fruit (fructose), refined sugar for baking (sucrose),
honey (fructose, glucose, maltose, sucrose)
These are digested by the body

Where is starch found?

In bread, pasta, rice, potatoes, sweet potatoes,etc.
Are digested by the body
Where is dietary fiber found?
In many plant foods (fruits and vegetables) and in whole grain foods
Cannot be broken down by the body (includes cellulose), but are important components of our diet

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