Carbohydrate

Definition: Carbohydrates are defined as polyhydroxy aldehyde or ketones or compound which

give them on hydrolysis. The term “carbohydrate” comes from the observation that when you

heat sugars, you get carbon and water (hence, hydrate of carbon). Carbohydrates have the

empirical formula (CH2O)n.

Biological importance of Carbohydrates

– They provide energy through oxidation.

– They supply carbon for the synthesis of cell components.

– They serve as a form of stored chemical energy.

– They form part of the structures of some cells and tissues.

• Carbohydrates, along with lipids, proteins, nucleic acids, and other compounds are known as

biomolecules because they are closely associated with living organisms.

Carbohydrates, in general, may be classified into two classes

(i) Sugars: These are crystalline substances which are sweet and water soluble. For example,

glucose, fructose and cane sugar.

(ii) Non-sugars: These are tasteless, insoluble in water and amorphous. For example. Starch,

cellulose, etc.
 Classes of Carbohydrates

1. Monosaccharides

2. Disaccharides

3. Oligosaccharides

4. Polysaccharides
 1. Monosaccharides

The word “Monosaccharides” derived from the Greek word “Mono” means single and

“saccharide” means sugar. Monosaccharides are polyhydroxy aldehydes or ketones which cannot

be further hydrolyzed to simple sugar. Monosaccharides are simple sugars. They are sweet in

taste. They are soluble in water. They are crystalline in nature. They contain 3 to 10 carbon

atoms, 2 or more hydroxyl (OH) groups and one aldehyde (CHO) or one ketone (CO) group.

Classification of Monosaccharides

Monosaccharides are classified in two ways-

A. Based on the functional group present: Those containing the aldehyde function,-CHO,

are called aldoses. Others containing the keto group, -CO-, are called ketoses. Example, Glucose

and Fructose.
B. Based on the numbers of Carbon atoms: By the number of Carbon atoms in the

molecule. These monosaccharides containing 3,4,5,6 etc., carbon atoms are designated as trioses,

tetroses, pentoses, hexoses, and so on.

The naturally occurring monosaccharides contain three to seven carbon atoms per molecule.

Monosaccharides of specific sizes may be indicated by names composed of a stem denoting the

number of carbon atoms and the suffix -ose. For example, the terms triose, tetrose, pentose,

andhexose signify monosaccharides with, respectively, three, four, five, and six carbon atoms.

Monosaccharides are also classified as aldoses or ketoses.

Those monosaccharides that contain an aldehyde functional group are called aldoses; those

containing a ketone functional group on the second carbon atom are ketoses. Combining these

classification systems gives general names that indicate both the type of carbonyl group and the

number of carbon atoms in a molecule. Thus, monosaccharides are described as aldotetroses,

aldopentoses, ketopentoses, ketoheptoses, and so forth. Glucose and fructose are specific

examples of an aldohexose and a ketohexose, respectively.

Trioses

Trioses are “Monosaccharides” containing 3 carbon atoms. The molecular formula of triose is

C3H6O3.
Characteristics

• Trioses are simple sugars

• They are soluble in water

• They are sweet in taste.

• The triose may contain an aldehyde group (aldotriose) or a ketone group (ketotriose). Example

Glycerose and Dehydroxyacetone.

Tetroses

Tetroses are “Monosaccharides” containing 4 carbon atoms. The molecular formula of tetrose is

C4H8O4.

Characteristics

• Tetroses are simple sugars

• Tetroses are soluble in water

• They are sweet in taste.

• They are crystalline forms.

• The tetroses may contain an aldehyde group

- Tetroses are simple sugars

- Tetroses are soluble in water

- They are sweet in taste. (ketotetrose).

 Pentoses

Pentoses are “Monosaccharides” containing 5 carbon atoms. It is an important component of

“nucleic acid”. The molecular formula of Pentose is C5H10O5.

Characteristics

• Pentoses are simple sugars

• Pentoses are soluble in water

• They are sweet in taste.

• They are crystalline forms.

• The pentoses may contain an aldehyde group (aldopentose) or a ketone group (ketopentose).

Hexoses

Hexoses are “Monosaccharides of Hexose is C6H12O6.

Characteristics

• Hexoses are simple sugars

• Hexoses are soluble in water

• They are sweet in taste.

• They are crystalline forms.

• The pentoses may contain an aldehyde group or ketone group (aldohexose / ketohexose).

Properties of monosaccharide

Monosaccharide exists in both as straight chain structure and cyclic structure (Figure). Sugars

with five membered rings and with six membered rings are most stable. Cyclic structures are the

result of hemiacetal formation by intermolecular reaction between carbonyl group and a

hydroxyl group.
 Pyranoses

The 6-member rings ("pyranoses") have a slightly different but quite similar Haworth projection.

A hexagon is placed so that one horizontal bond runs along the bottom. The oxygen in the ring

is placed at the upper right. Usually, the hemiacetal carbon (the anomeric position) is placed at

the extreme right. In solution, glucose, galactose, and mannose will exist as six member

pyranose rings. The sugar ring resembles the cyclic ether called pyran. Again, the bond at the

bottom is assumed to be coming out of the plane and vertical bonds are used to indicate

substituents above and below the 6-member ring.

Furanoses

We divide Haworth projections into two classes: Furanoses and Pyranoses. The furanoses or 5-

member ring hemiacetals are drawn with the oxygen at the top of a pentagon. The horizontal

bond at the bottom is assumed to be coming out of the plane toward you. Thus, the five-

member ring is in a plane perpendicular to the page. Vertical lines are drawn on each carbon to

indicate attachements above and below the plane of the 5-member ring. In solution, fructose,

ribose, and deoxyribose will exist as five member furanose rings. The furanose ring resembles

the cyclic ether called furan. A furanose form of the sugar ribose is a good example:
 1. Chiral center

All monosaccharide except dihydroxy acetone contain one or more asymmetric (chiral) carbon

atoms thus are optically active isomers (enantiomers). A molecule with n chiral centers can have

2n sterioisomers. Glyceraldehyde with one chiral center has 21=2 and glucose with four chiral

centres, have 24 =16 stereoisomers.

2. D and L isomerism

One of the two enantiomers of glyceraldehyde is designated the D isomers and the other L

isomers. If the OH on the bottom chiral centre points to the right, it is referred to as D and if the

OH on the bottom chiral centre points to the left, it is referred to as L. Most of sugars present in

biological system are D sugars. The D and L forms of glucose are shown in Figure.
 3. Anomers

In aqueous solution all monosaccharide with five or more carbon atoms in the backbone occur as

cyclic forms. Formation of cyclic structure is result of a reaction between alcohols and aldehydes

or ketones to form derivatives called hemiacetal or hemiketals. The ring structure of

monosaccharide are either similar to pyran (a six membered ring) or furan (a five membered

ring).

In linear form of monosaccharide, which is in equilibrium with the cyclic forms, the anomeric

carbon is easily oxidised, making the sugar a reducing sugar. D-glucose exists in solution as an

intramolecular hemiacetal in which the free –OH at C-5 has reacted with aldehyde C-1 producing

two anomers called α and β. D-fructose also forms hemiketal in which –OH at C-5 has reacted

with keto at C-2 producing two anomers called α and β (Figure).

In the cyclic form of a sugar, the anomeric carbon is the carbon that was part of the carbonyl

group in the straight-chain structure. The α form has the anomeric OH group at C-1 on the

opposite side of the ring from the CH₂OH group at C-5. The β form has the anomeric OH group

on the same side as the CH₂OH.

Isomeric forms of monosaccharide that differ only in their configuration about the hemiacetal or
hemiketal carbon atom are called anomers, and the carbonyl carbon atom is called the anomeric

carbon. The interconversion of α and β anomers in aqueous solution is called mutarotation, in

which one ring form opens briefly into the linear form, then closes again to produce β anomers.

Thus, a solution of β –D glucose and solution of α-D-glucose eventually form identical

equilibrium mixtures having identical properties. This mixture consists of about one third of α-

isomers and two third β-D-glucose.

4. Epimers

Isomers having different configuration of –OH only at one carbon atoms are known as epimers.

The most important epimers of glucose are mannose (epimers at C-2) and galactose (epimers at

C-4) (Figure).
 Isomers and epimers

Compounds that have the same chemical formula but have different structures are called isomers.

For example, fructose, glucose, mannose, and galactose are all isomers of each other, having the

same chemical formula C6H12O6. If two monosaccharides differ in configuration around only one
specific carbon atom (with the exception of the carbonyl carbon) they are defined as epimers of

each other. (they are also isomers!) For example-

 Glucose and galactose are C-4 epimers—their structures differ only in the position of the

-OH group at carbon 4.

 Glucose and mannose are C-2 epimers.

However, galactose and mannose are NOT epimers—they differ in the position of –OH groups at

two carbons (2 and 4) and are, therefore, defined only as isomers. [Note: The carbons in sugars

are numbered beginning at the end that contains the carbonyl carbon—that is, the aldehyde or

keto group].

Disaccharides

When two monosaccharides are combined together with elimination of a water molecule it is

called disaccharide. Monosaccharides are combined by glycosidic bond. If the glycoside or

acetol is formed by reaction of the anomeric carbon of a monosaccharide with OH group of

another monosaccharide molecule, then the glycoside product is a disaccharide.

The anomeric carbon can react with any of the hydroxyl groups of another monosaccharide unit

to form a disaccharide. Disaccharides can be categorized by the position of the hydroxyl group of
another monosaccharide making up the glycoside. Disaccharides have three naturally occurring

glycosidic linkages

• 1-4' link: The anomeric carbon is bonded to oxygen on C-4 of second monosaccharide.

• 1-6' link: The anomeric carbon is bonded to oxygen on C-6 of second monosaccharide.

• 1-2' link: The anomeric carbons of the two monosaccharide unit are bonded through oxygen.

The “prime” superscript indicates that –OH group bonded carbon position of the second

monosaccharide unit, α - and β -configuration given by based on the configuration at the

anomeric carbon of the first monosaccharide unit.

Disaccharides consist of two sugars joined by an O-glycosidic bond. The most abundant

disaccharides are sucrose, lactose and maltose. Other disaccharides include isomaltose,

cellobiose and trehalose.

On the basis of type of monomer sugar participating the formation of disaccharides they are of

two types as discussed below-

A. Homodisachharides

B. Heterodisachharides
 A. Homodisaccharides

a. Sucrose

Sucrose also called saccharose is ordinary table sugar refined from sugar cane or sugar beets.

Sucrose is formed when a monomer of glucose and a monomer of fructose are joined in a

dehydration reaction to form a glycosidic bond. In the process, a water molecule is lost. By

convention, the carbon atoms in a monosaccharide are numbered from the terminal carbon

closest to the carbonyl group. Sucrose is not a reducing sugar. This is because the glycosidic

linkage involves first carbon of glucose and second carbon of fructose, and hence there are no

free reducing groups. The Glycosidic linkage present in sucrose is between C−1 of α− glucose

and C−2 of β− fructose. When sucrose is hydrolyzed the resulting products have reducing

property.

b. Lactose

Lactose is a reducing sugar composed of one molecule of D-galactose and one molecule of D-

glucose joined by a β-1,4-glycosidic bond (the bond from the anomeric carbon of the first

monosaccharide unit being directed upward). Many adults and some children suffer from a

deficiency of lactase Milk products which contain lactose are converted to galactose and glucose
in the digestive track using an enzyme called lactase. People with lactose intolerance do not

produce very little or no lactase and the undigested lactose in the intestinal tract are metabolized

by bacteria releasing CO2 and other organic acids causing diarrhoea.

c. Maltose

Maltose consists of two molecules of glucose that are linked by an α-(1,4') glycosidic bond.

Maltose results from the enzymatic hydrolysis of amylose, a homopolysaccharide, by the enzyme

amylase. Maltose is converted to two molecules of glucose by the enzyme maltase, which

hydrolyzes the glycosidic bond.

Oligosaccharides
The oligosaccharides contain from 3 to 10 monosaccharide units (e.g., Raffinose). The Raffinose

is a oligosaccharide found in peas and beans; largely undigested until reaching the intestinal flora

in the large intestine, releasing hydrogen, carbon dioxide, and methane.

 General properties of carbohydrates

• Carbohydrates act as energy reserves, also stores fuels, and metabolic intermediates.

• Ribose and deoxyribose sugars forms the structural frame of the genetic material, RNA and

DNA.

• Polysaccharides like cellulose are the structural elements in the cell walls of bacteria and

plants.

• Carbohydrates are linked to proteins and lipids that play important roles in cell interactions.

• Carbohydrates are organic compounds, they are aldehydes or ketones with many hydroxyl

groups.

Function of Oligosaccharides

Lowering the intestinal pH, inhibiting the growth of spoilage bacteria and intestinal Salmonella,

regulating gastrointestinal function, inhibiting intestinal spoilage substances, changing stool

characteristics, preventing constipation, and increasing vitamin synthesis all help to improve

human immune function.

 i. Proliferation

One of the advantages of functional oligosaccharides is that they improve micro – ecological

environment in human body, allowing bactericidal and other beneficial bacteria to thrive.

ii. Blood Lipid Metabolism

Functional oligosaccharides, which are comparable to water – soluble plant fibres, can help to

enhance blood lipid metabolism and lower cholesterol and triglyceride levels.

Conclusion

Oligosaccharides (also known as oligose) are a form of functional sugar that is relatively new.

Since they integrate nutrition, diet therapy and health care to play a key role in boosting the

immune system, functional oligosaccharides are typically lower in calories and include useful

microorganisms. Food, health items, beverages, feed additives, medication, and other areas all

employ them. Oligosaccharide syrup, for example, can sweeten and thicken foods while also

giving a sticky gloss.

Polysaccharides
Polysaccharides contain hundreds or thousands of carbohydrate units. Polysaccharides are not

reducing sugars, since the anomeric carbons are connected through glycosidic linkages. They are

also called as “glucans”. Polysaccharides differ from each other in the identity of their recurring

monosaccharide units, in the length of their chains, in the types of bond linking units and in the

degree of branching. They are primarily concerned with two important functions i.e. structural

functions and the storage of energy.

Types of Polysaccharides

A. Homopolysaccharides: Homopolysaccharide is made up of one type of monosaccharide

unit.
B. Heteropolysaccharides: Heteropolysaccharides is made up of more than one type of

monosaccharide unit.

Starch
Starch is a polymer consisting of D-glucose units. Starches (and other glucose polymers) are

usually insoluble in water because of the high molecular weight, but they can form thick

colloidal suspensions with water. Starch is a storage compound in plants, and made of glucose

units. It is a homopolysaccharide made up of two components: amylose and amylopectin. Most

starch is 10-30% amylose and 70-90% amylopectin.

A. Amylose

Amylose is a linear component and it is made up of between 100-10,000 glucose monomers and these

are all linked by 1, 4 glycosidic bonds between α-D-glucose molecules.

The amylose chain forms a helix. Amylase plays a very deterministic role in the energy that is stored

by plants. When it is converted to amylopectin, it is not digested very easily, since amylase has a

helical shape that takes up less space as compared to the space taken up by amylopectin. Amylase

accounts for at least 30 percent of the starch that is stored in all plants. Amylase enzyme α-amylase

breaks it down further into maltose and maltotriose, and these give energy to the plants.

Properties

i. It is poorly water but forms micellar suspension.

ii. It has a variable molecular mass.

iii. When it reacts with iodine, forms a very distinct blue-colored compound.

iv. When exposed to hydrogen amylase molecules tend to form very tight bonds which make

these molecules less prone to enzymatic degradation.

B. Amylopectin

Amylopectin-a glucose polymer with mainly α - (1→4) linkages, but it also has branches formed

by α -(1→6) linkages. Branches are generally longer than shown above. Amylopectin differs

from amylose in being highly branched.

Short side chains of about 30 glucose units are attached with α-1→6 linkages approximately

every twenty to thirty glucose units along the chain. Amylopectin molecules may contain up to

two million glucose units. Amylopectin causes a red-violet color change on reaction with iodine.

The side branching chains are clustered together within the amylopectin molecule. This change is

usually masked by the much darker reaction of amylose to iodine.

 Properties

i. Starch is a white tasteless powder that’s insoluble in cold water, alcohol, or other

solvents.

ii. The basic formula to deduce starch is (C6H10O5)n, where n is the number of glucose

molecules in the chain.

iii. The breakdown of starch by dry heat forms pyrodextrins which are responsible for the

browning of bread.

Glycogen

Glycogen is storage homopolysaccharide of animals and is consist of glucose units linked by α

(1-4) glycoside linkage like amylopectin in starch. Branching is more extensive as compared to

amylopectin, occur every 8 to 14 glucose residues and linkage at the branch points is α-(1-6)

glycosidic. Each glycogen molecule contains up to 120,000 glucose units. Muscle cells contain

glycogen at 1-2% of their dry weight, and liver cells contain up to 10% of their dry weight as

glycogen, which is sufficient for >12 hour energy supply for the body.

Glycogen granules contain enzymes that catalyze glycogen synthesis and breakdown, as well as

enzymes that regulate these processes. Glycogen’s highly branched structure is physiologically

significant; it permits glycogen’s rapid degradation through the simultaneous release of the
glucose units at the end of every branch. In animals the fat is far more abundant in the body and

can serve the same purpose as glycogen but still body uses glycogen as storage energy. The

reason for that is-

a. Muscle cannot mobilize fat as rapidly as glycogen,

b. The fatty acid residues of the fat cannot be metabolized anaerobically, and

c. Animals cannot convert fatty acids to glucose, so fat metabolism alone cannot adequately

maintain essential blood glucose levels.

Cells can only metabolize glucose monomers but cannot store glucose within cells. Storage of

glucose monomers in the form of starch (in plants) and glycogen (in animals) greatly reduces the

large intracellular osmotic pressure that would result from its storage in monomeric form.

Osmotic pressure is proportional to the number of solute molecules in a given volume

The size and structure of glycogen suits its function

i. Its size makes it too large to cross cell membranes.

ii. The structure of glycogen solves the enormous of osmotic pressure within the cell.

iii. The high branch structure of glycogen simplifies the cell’s logistical problems.

Glucose (from glycogen) is highly water soluble and as an ideal source of “ready energy”.
 Cellulose

Cellulose is a homopolymer of glucose which is formed by beta 1-4 linkage of D-glucose units.

Cellulose is an organic compound, with the chemical formula as, (C6H10O5)n. It is a

polysaccharide, which contains a linear chain of many hundred to many thousands of β-(1→ 4)

units of the linked D-glucose. It is also an essential structural component of the primary cell wall

of the green plants, various algae forms, and the oomycetes. A few bacteria species secrete it to

form biofilms.

Cellulose is also the Earth's most abundant organic polymer. Cellulose content of the cotton fiber

is 90%, that of dried hemp is approximately 57%, where that of wood is 40-50%.Cellulose

(glucan) chains aggregate after synthesis and are connected by hydrogen bonds to form strong

bundles known as microfibrils. Cellulose is insoluble in water and most organic solvents and can

be collected as the residue after alkali extraction of hemicelluloses. Humans cannot digest

cellulose because they do not have the enzymes to break these bonds.
 Properties

i. Cellulose is tasteless and odorless.

ii. Cellulose is insoluble in water and soluble in organic solvents.

iii. It’s a crystalline solid with a white powdery appearance. It requires a temperature of

320°C and pressure of 25 MPa to become amorphous in water.

iv. The plant cellulose exhibits 60% water retention values, whereas bacterial cellulose

exhibit 1000% water retention of the cellulose sample weight.

v. Cellulose has a high tensile strength (like steel) resulting from an alternate arrangement

of glucose molecules in its structure.

vi. It can be broken down into glucose monomer units by treating it with concentrated

mineral acids at high temperatures.

vii. The process of degradation of cellulose is known as cellulolysis and the breakdown of

cellulose, when exposed to high temperature, is called thermolysis.

Cellulose is primarily used to produce paper and paperboard. The smaller quantities of Cellulose

are converted into a wide variety of derivative products such as Rayon and cellophane.

Conversion of Cellulose from the energy crops into biofuels like cellulosic ethanol is under

development as a renewable fuel source.

 Peptidoglycan
The term peptidoglycan has been derived from the peptides and the sugars (glycan) that make a

molecule; it is also called ‘murein’ or ‘mucopeptide.’ This complex interwoven network of sugar

polymer and amino acids surrounds the entire bacterial cell. It provides structural rigidity and

gives characteristics shape for the bacteria. Peptidoglycan is found only in bacterial cell walls but

not in human cells. Archaea do not have a cell wall consisting of peptidoglycan, but some do

have a layer of pseudopeptidoglycan (pseudomurein), which is similar polymer.so it is regarded

as a key biomarker of bacteria. Peptidoglycan is a good target for antibacterial drugs such as

penicillins, cephalosporins, and vancomycin, which inhibit the synthesis of peptidoglycan by

inhibiting transpeptidase reactions.

Structure of Peptidoglycan
Peptidoglycan consists of a carbohydrate backbone (glycan chain) composed of alternating units

of N-acetylglucosamine (NAG) and N-Peptidoglycan consists of a carbohydrate backbone

(glycan chain) composed of alternating units of N-acetylglucosamine (NAG) and N-

acetylmuramic acid (NAM) molecules attached through β-1,4-glycosidic bonds. The covalent

bonds between NAG-NAM form a sheet-like structure around the bacterium.

Multiple such sheet-like structures are cross-linked with each other by tetrapeptides. This cross-

linking provides rigidity to the bacterial cell, the strength of which depends on the frequency of

cross-links present. Each muramic acid of a glycan chain contains a tetrapeptide consisting of

both D- and L- amino acids. L-alanine, D-glutamic acid, lysine or its structural analog

diaminopimelic acid (DAP), and D-alanine are found in those tetrapeptides. The presence of two
amino acids of the D stereoisomer; D -alanine and D -glutamic acid, is the unique feature of

peptidoglycan. Proteins, by contrast, always consist of L -amino acids

Properties

i. It is degraded by an enzyme, lysozyme, that causes the hydrolysis of beta-1,4-linkage

between N-acetylglucosamine (NAG) and N-acetylmuramic acids (NAM).

ii. The production of peptidoglycans can be interfered with by using penicillin.

iii. N-Acetylmuramoyl-L-alanine amidases are enzymes that cause the hydrolysis of

peptidoglycans and the dissolution of their structure.

Difference between Peptidoglycan and Proteoglycan

i. Peptidoglycan should not be confused with the similar-sounding word proteoglycan.

While peptidoglycan refers to the bacterial cell wall, a proteoglycan is a protein that has been

glycosylated, which means that it has had carbohydrates attach to it.

ii. Proteoglycans are found in connective tissue, a category which includes cartilage, bone,

blood, fibrous tissues, and adipose tissue (fat).

Function of Peptidoglycan
i. Peptidoglycan is a polymer of amino acids and sugars making up the cell walls of

bacteria.

ii. This basic unit of the cell wall in bacteria presents the cell with mechanical rigidity,

structural strength.

iii. It also safeguards the cytoplasmic membrane and helps identify the cell form.

iv. They are also involved in counteracting the osmotic pressure of the cytoplasm. It also

participates in binary fission during the cell reproduction seen in bacteria.

 Medical Significance of Peptidoglycan
i. Peptidoglycan is a good target for antibacterial drugs. Drugs like penicillin

scephalosporins, etc inhibit transpeptidase reaction (which makes cross-links between the two

adjacent tetrapeptides) involved in peptidoglycan synthesis.

ii. Lysozyme enzymes in human tears, mucus, and saliva cleave the peptidoglycan

backbone, breaking the glycosyl bonds of peptidoglycan, thus providing a major line of defense

against bacterial infection.

iii. Gram-positive bacteria are generally resistant to complement-mediated lysis because the

thick peptidoglycan layer in their cell wall prevents the insertion of the membrane attack

complex (MAC) into the inner membrane.