Carbohydrates

Syllabus:
Structure and biological importance of derived monosaccharides-amino sugars,
sugar acids sugar phosphates-oligosaccharides-isomaltose, cellobiose,
trehalose-polysaccharides-starch, glycogen and cellulose.
Heteropolysaccharides-Occurrence and composition of Hyaluronic
acid-chondroitin and its sulphates-dermatan sulphate-heparin-agar-agar.
• What are carbohydrates?
• Carbo (carbon) hydrate (water) - Cn(H2O)n
• Carbohydrates are produced in plants through Photosynthesis

• CO2 + H2O + --> carbohydrates + O2

cellulose (structural components)
starch (energy reserve)
• Carbs in Humans
• Carbohydrate oxidation --> chemical & heat energy
• Carbohydrate storage = glycogen (energy reserve)
• Carbohydrates provide C atoms for synthesis of proteins, nucleic acids
& lipids
• Carbohydrates are important in structure of DNA & RNA
• Carbohydrates can be linked with lipids & proteins
 Types of Carbohydrates
• All carbohydrates are polyhydroxy aldehydes (PA - ex: glucose) or ketones (PK - ex:
fructose) or compounds that hydrolyze to produce them.
• Monosaccharides
• Composed of ONE PA or PK unit
• Monomers for larger carbohydrates that are formed by condensation reactions aldohexose

• Simplest- Trioses: 2,3-dihydroxypropanal & dihydroxypropanone

• Disaccharides - 2 monomer units
• Oligosaccharides
• Composed of 3 - 10 monosaccharide units
• Humans can’t digest most of these; bacteria in colon do (producing large ketohexose

quantities of CO2 gas)

• Polysaccharides
• Composed of “many” monosaccharide units
Fischer projections and common names for D-aldoses three, four, five,
and six carbon atoms.
• Derived monosaccharides:

• These are derivatives of monosaccharides that contain functional group in addition to the

carbonyl and hydroxyl groups.

• Some derivatives of the monosaccharides are:

Phosphoric acid esters of monosaccharides.

Amino sugars

Deoxy sugars

Sugar acids

Sugar alcohols
Amino sugars:
• These are monosaccharides in which hydroxyl group is replaced by an amino or acetyl amino group.
• Generally the hydroxy groups on the carbon-2 is replaced by amino or N-acetyl amino group.
• The commonest amino sugars are D-Glucosamine and D-Galactosamine.

D-Glucosamine D-Galactosamine

N-Acetyl glucosamine N-Acetyl galactosamine

 D-Glucosamine

• D-Glucosamine is present in Chitin, hyaluronic acid etc. in various forms viz. acetylated, sulfonated etc.
• It is produced in industrial scale by hydrolysis of chitin. It is available in the form of salts like glucosamine
hydrochloride, glucosamine sulphate potassium etc.
• It is also produced by fermentation of corn or wheat.
• It is used as a dietary supplement for arthritis. But this is not a prescription drug since there is little evidence
for its effect on relief of arthritis.
• It is marketed as a supplement to support the structure and function of joints, and the marketing
is targeted to people suffering from osteoarthritis.
 Galactosamine

• It is a constituent of some glycoprotein hormones such as follicle-stimulating

hormone (FSH) and luteinizing hormone (LH).
• It is a hepatotoxic agent.
• It is sometimes used in animal models of liver failure.
 N-Acetyl glucosamine

• N-Acetylglucosamine is an amide derivative of the monosaccharide glucose.

• It is part of a biopolymer in the bacterial cell wall.
• It is the monomeric unit of the polymer chitin and hence can be obtained by partial
hydrolysis of chitin.
• It forms hyaluronic acid on polymerization with glucuronic acid.
• It has been proposed as a treatment for autoimmune diseases
 N-Acetyl galactosamine

• N-Acetylgalactosamine is necessary for intercellular communication, and is concentrated

in sensory nerve structures of both humans and animals.

• In humans it is the terminal carbohydrate forming the antigen of blood group A.

 Sugar acids
• Sugar acids are carboxylic acids of monosaccharides in which one or both the terminal carbon atoms
are oxidized to carboxylic acid groups.
• In aldonic acid C-1 is oxidized to acid. Example D-Gluconic acid.

• In uronic acid C-6 is oxidized to acid. Example: D-Glucuronic acid.

• In aldaric acid both C-1 and C-6 are oxidized. Example: Glucaric acid
 Biological importance

Gluconic acid:
• It is used to introduce cations like Ca+2 in to system ( as tablets). Because it
forms water soluble salts.
• Its phosphate derivative is an intermediate in the pentose phosphate pathway.

Glucuronic acid:
• It can convert many water-insoluble substances to water-soluble derivatives thereby
enabling detoxification of the body.
• Many naturally occurring substances (steroids, pigments etc.) and drugs (morphine,
salicylic acid, menthol etc.) are excreted in urine and bile by conjugation with glucuronic
acid.
• It is also part of polysaccharides like hyaluronic acid, chondroitin sulfate etc.
• Its derivative L-iduronic acid is found in heparin.

Galacturonic acid:
• It is a component of fruit pectin. Vitamin-C is a sugar acid of great biological importance
(though it has no acid group it is acid).
 Sugar phosphates

• These are esters of phosphoric acid with sugars which are the result of phosphorylation of sugars in biological
reactions.
• One or more of the hydroxyl groups of the sugar is substituted by phosphate groups.
• The phosphate group may be esterified at C-1 or C-6.
 Biological importance

• For sugars like glucose, fructose etc. to be metabolised in cell, they first have to be converted to their

phosphates by phosphorylation using ATP.

• The sugar phosphates are ionized at physiological pH due to their phosphate groups. This is important

in their retention in cell, as the sugars themselves can move through cell membrane in both directions.

• In general sugar phosphates are intermediate in carbohydrate metabolism within cells.

• Oligosaccharides

• Oligosaccharides are important group of polymeric carbohydrates that are found in all
living organisms.
• Oligosaccharides composed of 2 to10 monosaccharide residues.
• These monosaccharide's linked together by glycoside (α-1,4 or α-1,6 ) bonds.
• The discovery of new enzymes helps in developing other oligosaccharides of
monosaccharide's with other linked bonds.
• Trehalose (α,α 1,1), Gentio-oligosaccharides (β-1,6), Nigero-oligosaccharides (α-1,3),
Cyclodextrin (α-1-4).

16
 Oligosaccharides Substrates
Oligosaccharides Substrate
• Fructo-oligosaccharide Sucrose/Innulin.
• Malto- oligosaccharide Starch.
• Isomalto-oligosaccharide Starch.
• Galacto-oligosaccharide Lactose.
• Lactosucrose Lactose+ sucrose.
• Lactulose Lactose.
• Xylo- oligosaccharide Xylan.
• Soy- oligosaccharide Soy.

17
Properties

• Low sweetness intensity (1/3 of sucrose )

• Calorie free.
• Resistance to hydrolysis by digestive enzymes.
• Non-cariogenic (inhibit the growth of Streptococcus mutans)
• Highly soluble than sucrose.
• Heat stable (doesn't degrade by heating process)
• Hydrolyze in high acid environment.

18
 Benefits
• Prebiotic (enhance befidus bacteria in colon).
• Increase digestion of lactose metabolism.
• Increase mineral absorption.
• Increase HDL/LDL ratio.
• Decrease serum lipids and blood cholesterol.
• Decrease blood pressure.
• Decrease glycemic response.
• Decrease fecal pH, toxic, and carcinogenic
metabolites.
19
• Linkages in Oligosaccharides:

• A glycosidic bond is formed between the hemiacetal or hemiketal group of a saccharide

(or a molecule derived from a saccharide) and the hydroxyl group of some compound
such as an alcohol.
• An α-glycosidic bond is formed when both carbons have the same stereochemistry
In the case of maltose, the glycosidic bond is specified as α(1→4) and is simply stated as
alpha-one-four.

20
• β-glycosidic bond occurs when the two carbons have different stereochemistry.
• If the –OH group had been in the beta configuration when the glycosidic bond was
formed, the bond would be in the β(1→4) configuration. The molecule formed would be
named cellobiose and would have a different two-dimensional and three-dimensional.
 Isomaltose

• It is a reducing disaccharide formed by partial hydrolysis of amylopectin and glycogen.

• It consists of two glucose units linked by an α (1-6) glycosidic linkage.
• It is used as a low-calorie sweetener mixed with a variety of other food and beverage
products for the purpose of sweetening.
 Cellobiose

• It is a reducing disaccharide composed of two glucose units

• It consists of β(1-4) glycosidic linkage.
• It is obtained by incomplete acid hydrolysis of cellulose.
• It can be used as an indicator carbohydrate for Crohn's disease and malabsorption syndrome.
 Trehalose

• It is a non-reducing disaccharide composed of two glucose units.

• It consists of α (1-1) glycosidic linkage.
• Some bacteria, fungi, plants and invertebrate animals synthesize it as a source of energy, and to
survive freezing and lack of water.
• This is the major sugar of insect hemolymph and is found in mushrooms, algae and other fungi.
• It has high water retention capabilities, and is used in food, cosmetics and as a drug.
Polysaccharides
Polysaccharides are long chains of monosaccharides connected by glycosidic linkages.
• There are two types of polysaccharides:
1. Storage polysaccharides contain only α-glucose units. Three important ones are
starch, glycogen, and amylopectin.
2. Structural polysaccharides contain only β-glucose units. Two important ones
are cellulose and chitin. Chitin contains a modified β-glucose unit.
• Storage and structural polysaccharides are made up of glucose units, but they are
structurally and functionally different because of their glycosidic bonds and
difference in branching.

25
Storage Polysaccharides
Starch
• It is the storage polysaccharide of plant and is the main energy source in human diet.
• It is a mixture of unbranched amylose and branched amylopectin and is found in plant foods.
• Amylose makes up 20% of plant starch and is made up of 250–4000 D-glucose units bonded α(1→4) in a
continuous chain. The linear amylose molecules form compact helices in water that suit it for its storage
function.
• Molecular iodine can insert itself in to these helices to form a complex which is intensely blue.
• On partial enzymic or acid hydrolysis it yields glucose and maltose.
• Long chains of amylose tend to coil.

Amylose
26
 Helical Structure of Starch (Amylose)
• The most stable three-dimensional structure for the α(1 4) linked chains of starch and glycogen is a tightly
coiled helix.
• The helix is stabilized by interchain hydrogen bonds. The glucose residues in the chain are also able to form
hydrogen bonds to the surrounding solvent, which keep the polymer in solution.
• The average plane of each residue along the amylose chain forms a 60˚ angle with the average plane of the
preceding residue, so the helical structure has six residues per turn. These tightly coiled helical structures
produce the dense granules of stored starch or glycogen seen in many cells.
 Amylopectin

• Amylopectin makes up 80% of plant starch and is made up of D-glucose units connected by α(1→4)
glycosidic bonds.
• Amylopectin also has straight chains of glucose joined by α (1-4) linkage. However, once in every 24-30
units, branch points occur with α (1-6) linkages giving rise to side chain.
• Thus amylopectin has branched structure which consists of between a few thousand to a million glucose units.
It may have a molecular weight of several millions.
• With iodine it gives a red to purple color.
• Partial enzymic hydrolysis yields glucose, maltose and isomaltose.
 Glycogen
• Glycogen is a storage polysaccharide found in all cells but
especially present in liver cells (8-10% of wet weight) and
muscle cells (2 -3 % of wet weight)
• Its structure is identical to amylopectin, except that α(1→6)
branching occurs about every 8 - 10 glucose units average at
the peripheral parts of the molecule.
• At the interior of the molecule, branch points are more
frequent, occurring as often as every four units.
• When glucose is needed, glycogen is hydrolyzed in the liver to
glucose.
• It allows rapid mobilization of the glucose whenever required
by the body.
• On partial hydrolysis it yields glucose, maltose and isomaltose.
30
 Cellulose

• Cellulose is a structural polysaccharide present in plant cell wall.

• It is the most abundant organic compound on earth constituting more than half of the carbon in biosphere.
• It is a linear polymer of up to 15000 D-glucose units joined by β(1→4) glyosidic linkage.
• On hydrolysis it yields glucose and cellobiose.
• Humans and animals can’t digest cellulose due lack of enzyme required for its digestion in the body.
• Ruminant animals and termites have symbiotic organisms in their digestive system which produces the enzyme
cellulase which breaks cellulose.
• Adjacent straight chains of cellulose are held together by hydrogen bonds to form a sheet like strips called microfibrils.
• Many sheets are stacked one above the other to form macro fibrils.
• The whole assembly is stabilized by intermolecular hydrogen bonding.
• This highly cohesive structure makes cellulose fibres water insoluble and gives them unexceptional tensile strength.
Heteropolysaccharides
 Hyaluronic acid

• Hyaluronic acid is an anionic, non sulfated glycosaminoglycan distributed widely throughout connective,
epithelial, and neural tissues.
• It is composed of D-glucuronic acid and N-Acetyl-D-Glucosamine linked via alternating β-(1→4) and
β-(1→3) glycosidic bonds. It can be 25,000 disaccharide repeats in length.
• Hyaluronic acid is a main component of the extracellular matrix, and has a key role in tissue regeneration,
inflammation response, and angiogenesis (formation of blood vessels), which are phases of skin wound
repair.
• In gel form, hyaluronic acid combines with water and swells, making it useful in skin treatments as a
dermal filler (skin boosting) for treating facial wrinkles and lasting some 6 to 12 months.
 Chondroitin sulfate

R1 = H; R2 = SO3H; R3 = H. Chondroitin-6-sulfate: R1 = SO3H; R2,

R3 = H.

• Chondroitin sulfate (CS) is a linear heteropolysaccharide consisting of repeating disaccharide units of

N-acetyl-d-galactosamine and d-glucuronic acid connected by β-1,3 and β-1,4 glycosidic linkages, which is
commonly sulfated at C-4 and/or C-6 of galactosamine.
• It is a glycosaminoglycan (GAG) covalently linked to proteins forming proteoglycans (PGs).
• A chondroitin chain can have over 100 individual sugars, each of which can be sulfated in variable positions
and quantities.
• Chondroitin sulfate is an important structural component of cartilage and provides much of its resistance to
compression.
• Chondroitin sulfate is widely used dietary supplement along with glucosamine for treatment of osteoarthritis.
 R1 = H; R2 = SO3H; R3 = H. Chondroitin-6-sulfate: R1 = SO3H; R2,
R3 = H.

• Chondroitin sulfate chains are unbranched polysaccharides of variable length containing two alternating
monosaccharides: D-glucuronic acid (GlcA) and N-acetyl-D-galactosamine (GalNAc).
• Most chondroitin appears to be made from extracts of cartilaginous cow and pig tissues (cow trachea and
pig ear and nose), but other sources such as shark, fish, and bird cartilage are also used.
• Since chondroitin is not a uniform substance, and is naturally present in a wide variety of forms, the
precise composition of each supplement will vary.
• It is an essential component of cartilage and plays an important role in the elasticity and function of
articular cartilage where it is mainly attached covalently to core proteins in the form of proteoglycans.
 Dermatan sulfate

• Dermatan sulfate, also known as chondroitin sulfate B (CS-B), is composed of linear polysaccharides
assembled as disaccharide units containing , N-acetyl galactosamine (GalNAc) or glucuronic acid (GlcA)
joined by β (1,4) or (1,3) linkages respectively.
• It is found mostly in skin, but also in blood vessels, heart valves, tendons, and lungs.
• Dermatan sulfate may have roles in coagulation, cardiovascular disease, carcinogenesis, infection, wound
repair, maintains the shape of galactosamine 4-sulfate skin and fibrosis.
 Heparin

• Heparin is a naturally occurring glycosaminoglycan, produced by basophils and mast cells in all mammals.
• Its heterogeneous structure is made up of α-l-iduronic acid, β-d-glucuronic acid and a-d-glucosamine repeat units.
• It is used to decrease the clotting ability of the blood and help prevent harmful clots from forming in blood vessels.
• Specifically it is used in the treatment of heart attacks and unstable angina.
• It consists of a variably sulfated repeating disaccharide unit.
• The most common disaccharide unit is composed of a 2-O-sulfated iduronic acid and 6-O-sulfated, N-sulfated
glucosamine, IdoA(2S)-GlcNS(6S).
 Agar-Agar

• Agar-agar is a jelly-like substance, obtained from red algae.

• It is a mixture of two components: the linear polysaccharide agarose, and a heterogeneous mixture of smaller molecules
called agaropectin.
• Agarose is a linear polymer, made up of repeating units of agarobiose, a disaccharide made up of D-galactose and
3,6-anhydro-L-galactopyranose.
• Agaropectin is a heterogeneous mixture of smaller molecules that occur in lesser amounts, and is made up of alternating
units of D-galactose and L-galactose heavily modified with acidic side-groups, such as sulfate and pyruvate.
• It forms the supporting structure in the cell walls of certain species of algae (agarophytes), and is released on boiling.

Agarose Agaropectin