Erick Awuoche

§ A carbohydrate (saccharide) is an organic compound with the empirical

formula (CH2O)n (where n is greater than or equal to 3); that is, carbohydrate
consists only of carbon, hydrogen, and oxygen, with a hydrogen:oxygen atom
ratio of 2:1. some also contain nitrogen, phosphorus, or sulfur.
§ Carbohydrates can be viewed as hydrates of carbon, hence their name.
Structurally however, it is more accurate to view them as polyhydroxy
aldehydes and polyhydroxy ketones or derivatives of ketones; or substances
that yield such compounds on hydrolysis.
§ They are present in humans, animal tissues, plants and in micro-organisms; and
are also present in tissue fluids, blood, milk, secretions and excretions of
animals.
§ Are the most abundant biomolecules on Earth. Each year, photosynthesis
converts more than 100 billion metric tons of CO2 and H2O into cellulose and
other plant products.
§ Certain carbohydrates (sugar and starch) are a dietary staple in most parts of
the world, and the oxidation of carbohydrates is the central energy-yielding
pathway in most non-photosynthetic cells.
§ Insoluble carbohydrate polymers serve as structural and protective elements in
the cell walls of bacteria and plants and in the connective tissues of animals.
§ Other carbohydrate polymers lubricate skeletal joints and participate in
recognition and adhesion between cells.
§ More complex carbohydrate polymers covalently attached to proteins or lipids
act as signals that determine the intracellular location or metabolic fate of these
hybrid molecules, called glycoconjugates.
i. Carbohydrates are the major source of energy for man. For example,
glucose is used in the human body for energy production.
ii. Some carbohydrates serve as reserve food material in humans and in
plants. For example, glycogen in animal tissue and starch in plants serves as
reserve food materials.
iii. Carbohydrates are components of several animal structure and plant
structures. In animals, carbohydrates are components of skin, connective
tissue, tendons, cartilage and bone. In plants, cellulose is a component of
wood and fiber.
iv. Some carbohydrates are components of cell membrane and nervous tissue.
v. Carbohydrates are components of nucleic acids and blood group
substances.
vi. Carbohydrates are involved in cell-cell interaction.
vii. Derivative of carbohydrates are drugs. For example, a glycoside ouabain is
used in clinical medicine. Streptomycin an antibiotic is a glycoside.
viii. Aminosugars, derivatives of carbohydrates are components of antibiotics
like erythromycin and carbomycin.
ix. Ascorbic acid, a derivative of carbohydrate is a water-soluble vitamin.
x. Bacterial invasion involves hydrolysis of mucopolysaccharides.
xi. Survival of Antarctic fish in icy environment is due to presence of anti-freeze
glycoproteins in their blood.
§ There are three major size classes of carbohydrates: monosaccharides,
oligosaccharides, and polysaccharides (the word “saccharide” is derived from
the Greek sakcharon, meaning “sugar”).
§ Monosaccharides, or simple sugars, consist of a single polyhydroxy
aldehyde or ketone unit. The most abundant monosaccharide in nature is the
six-carbon sugar D -glucose, sometimes referred to as dextrose.
Monosaccharides of more than four carbons tend to have cyclic structures.
§ Oligosaccharides consist of short chains of monosaccharide units, or
residues, joined by characteristic linkages called glycosidic bonds. The most
abundant are the disaccharides, with two monosaccharide units. Typical is
sucrose (cane sugar), which consists of the six-carbon sugars D -glucose and D
-fructose. All common monosaccharides and disaccharides have names
ending with the suffix “-ose.”
§ In cells, most oligosaccharides consisting of three or more units do not occur
as free entities but are joined to nonsugar molecules (lipids or proteins) in
glycoconjugates.
§ The polysaccharides are sugar polymers containing more than 20 or so
monosaccharide units, and some have hundreds or thousands of units. Some
polysaccharides, such as cellulose, are linear chains; others, such as glycogen,
are branched. Both glycogen and cellulose consist of recurring units of D -
glucose, but they differ in the type of glycosidic linkage and consequently
have strikingly different properties and biological roles.
§ Monosaccharides are those carbohydrates which can not be
hydrolyzed to small compounds.
§ Their general formula is Cn(H2O)n . They are also called as simple
sugars.
§ Monosaccharides containing three to nine carbon atoms occur in
nature.
Nomenclature
§ Monosaccharides are classified according to three different
characteristics:
§ The placement of its carbonyl group (functional group): If the carbonyl
group is an aldehyde (CHO), the monosaccharide is an aldose; if the
carbonyl group is a ketone (CO), the monosaccharide is a ketose.
§ The number of carbon atoms it contains: Monosaccharides with three
carbon atoms are called trioses, those with four are called tetroses, five are
called pentoses, six are hexoses, and so on
§ Its chiral handedness. These two systems of classification are often
combined. For example, glucose is an aldohexose (a six-carbon aldehyde),
ribose is an aldopentose (a five-carbon aldehyde), and fructose is a
ketohexose (a six-carbon ketone).
§ Some important monosaccharides (systematic names are given
in parenthesis)
§ All the monosaccharides except dihydroxyacetone contain at least one
asymmetric (chiral) carbon atom and hence they exhibit optical
isomerism.
§ The two optical isomers of glyceraldehyde containing one asymmetric
carbon atom are D-glyceraldehyde and L-glyceraldehyde. The optical
isomers are also called as enantiomers. The D and L forms of
glyceraldehyde.
§ Further D and L-glyceraldehyde are used as parent compounds to
designate all other sugars (compounds) as D or L forms. If a sugar has
the same configuration as D glyceraldehyde on the penultimate carbon
atom then it is called as ‘D’ sugar. If a sugar has the same configuration
as L-glyceraldehyde on the penultimate carbon atom then it is called as
‘L’ sugar.
§ Usually, the hydroxyl group on penultimate carbon atom points to right
in ‘D’ glucose and D-glyceraldehyde whereas it points to left in L-
glucose and L-glyceraldehyde.
§ Further D and L forms of glucose are mirror images like mirror images
of glyceraldehyde. Though both forms of sugars are present in nature D-
isomer is abundant and sugars present in the body are all D-isomers. L-
fructose and L-rhamnose are two L-isomers found in animals and plants.
§ Monosaccharides except dihydroxy acetone exhibit optical
activity because of the presence of asymmetric carbon atom.
§ If a sugar rotates plane polarized light to right then it is called
as dextrorotatory and if a sugar rotates the plane polarized
light to the left then it is called as levorotatory.
§ Usually ‘+’ sign or ‘d’ indicates dextrorotation and ‘–’ sign or 1
indicates levorotation of a sugar.
§ For example, D-glucose which is dextrorotatory is designated
as D(+) glucose and D-fructose, which is levorotatory is
designated as D(–) fructose.
§ The letter ‘D’ does not indicate whether a given sugar is dextro
or levorotatory.
§ Two sugars that differ only in the
configuration around one carbon atom
are called epimers.
§ Are those monosaccharides that differ in
the configuration of –OH group on 2nd, 3rd
and 4th carbon atoms.
§ Epimers are also called as
diastereoisomers. Glucose, galactose
and mannose are examples for epimers.
§ Galactose is an epimer of glucose
because, configuration of hydroxyl group
on 4th carbon atom of galactose is
different from glucose.
§ Similarly, mannose is an epimers of
glucose because configuration of
hydroxyl group on 2nd carbon atom of
mannose is different from glucose.
§ Ribulose and xylulose are also epimers.
They differ in the configuration of –OH
group on third carbon atom
§ Functional isomers have same molecular formulae but differ in
their functional groups.
§ For example, glucose and fructose have same molecular
formulae C6H12O6, but glucose contains aldehyde as functional
group and fructose contains keto group.
§ Hence, glucose and fructose are functional isomers. This type of
functional isomerism is also called as aldoseketose
isomerism because aldose is an isomer of ketose and vice
versa.
§ For simplicity, the structures of monosaccharides aldoses and ketoses are
represented as straight-chain molecules.
§ In fact, in aqueous solution, aldotetroses and all monosaccharides with five or
more carbon atoms in the backbone occur predominantly as cyclic (ring)
structures in which the carbonyl group has formed a covalent bond with the
oxygen of a hydroxyl group along the chain.
§ The formation of these ring structures is the result of a general reaction
between alcohols and aldehydes or ketones to form derivatives called
hemiacetals or hemiketals, which contain an additional asymmetric carbon
atom and thus can exist in two stereoisomeric forms.
§ For example, D –glucose exists in solution as an intramolecular hemiacetal in
which the free hydroxyl group at C-5 has reacted with the aldehydic C-1,
rendering the latter carbon asymmetric and producing two stereoisomers,
designated a and ℬ. These six-membered ring compounds are called
pyranoses because they resemble the six membered ring compound pyran.
The systematic names for the two ring forms of D -glucose are -D -
glucopyranose and ℬ -D -glucopyranose.
§ Aldohexoses also exist in cyclic forms having five membered rings, which,
because they resemble the five membered ring compound furan, are called
furanoses. However, the six-membered aldopyranose ring is much more stable
than the aldofuranose ring and predominates in aldohexose solutions. Only
aldoses having five or more carbon atoms can form pyranose rings.
§ An aldehyde or ketone can react with an alcohol in a 1:1 ratio to yield a
hemiacetal or hemiketal, respectively, creating a new chiral center at the
carbonyl carbon.
§ Substitution of a second alcohol molecule produces an acetal or ketal.
When the second alcohol is part of another sugar molecule, the bond
produced is a glycosidic bond
§ Reaction between the
aldehyde group at C-1 and
the hydroxyl group at C-5
forms a hemiacetal linkage,
producing either of two
stereoisomers,
the and anomers, which
differ only in the
stereochemistry around the
hemiacetal carbon.
§ The interconversion
of and anomers is called
mutarotation.
§ The six-membered pyranose ring is not
planar, as Haworth perspectives
suggest, but tends to assume either of
two “chair” conformations.
§ Two conformations of a molecule are
interconvertible without the breakage
of covalent bonds, whereas two
configurations can be interconverted
only by breaking a covalent bond—for
example, in the case of α and β
configurations, the bond involving the
ring oxygen atom.
§ The specific three-dimensional
conformations of the monosaccharide
units are important in determining the
biological properties and functions of
some polysaccharides
§ Those monosaccharides that differ in configuration of OH groups
on carbonyl carbon or anomeric carbon are called as anomers.
§ Formation of ring structure of glucose generates anomers of
glucose, which are designated as α and β forms.
§ These two forms of glucose differ in the configuration of OH on
carbonyl carbon or 1st carbon atom.
§ In the α-form the hydroxyl group on anomeric carbon (1st carbon)
atom points to the right where as in the β -form to the left.
§ Monosaccharides containing asymmetric carbon atom rotate plane
polarized light.
§ When optical rotation for α -D-glucose is measured it will be 112°
and on standing the rotation decreases slowly and attains a
constant value +52.5°.
§ Likewise when optical rotation for β -D-glucose is measured the
rotation changes from initial +19° to +52.5°.
§ The change in optical rotation when either form of glucose is
allowed to stand in solution is called mutarotation. It is due to
conversion of cyclic form of glucose to straight chain form.
§ Monosaccharides can be oxidized by relatively mild oxidizing
agents such as ferric (Fe3 ) or cupric (Cu2 ) ion. The carbonyl
carbon is oxidized to a carboxyl group. Glucose and other
sugars capable of reducing ferric or cupric ion are called
reducing sugars.
§ This property is the basis of Fehling’s reaction, a qualitative
test for the presence of reducing sugar. By measuring the
amount of oxidizing agent reduced by a solution of a sugar, it is
also possible to estimate the concentration of that sugar.
§ For many years this test was used to detect and measure
elevated glucose levels in blood and urine in the diagnosis of
diabetes mellitus.
§ Now, more sensitive methods for measuring blood glucose
employ an enzyme, glucose oxidase
§ Sugars as reducing agents. (a) Oxidation of the anomeric carbon of glucose and
other sugars is the basis for Fehling’s reaction. The cuprous ion (Cu) produced under
alkaline conditions forms a red cuprous oxide precipitate. In the hemiacetal (ring)
form, C-1 of glucose cannot be oxidized by Cu2. However, the open-chain form is in
equilibrium with the ring form, and eventually the oxidation reaction goes to
completion. The reaction with Cu2 is not as simple as the equation here implies; in
addition to D-gluconate, a number of shorter-chain acids are produced by the
fragmentation of glucose.
§ (b) Blood glucose concentration is commonly determined by measuring the amount
of H2O2 produced in the reaction catalyzed by glucose oxidase. In the reaction
mixture, a second enzyme, peroxidase, catalyzes reaction of the H2O2 with a colorless
compound to produce a colored compound, the amount of which is then measured
spectrophotometrically.
§ Important monosaccharides in the metabolic point of view are
glucose, fructose, galactose, ribose, erythrose and
glyceraldehyde.
§ Glucose is found in several fruit juice blood of humans and in
honey.
§ Galactose is a part of lactose.
§ Fructose is found in several fruit juices and honey.
§ Commonly glucose is referred as dextrose.
§ All monosaccharides containing free aldehyde or keto group
reduces ions like Cu2+ under alkaline conditions.
§ Sugar derivatives of biological importance are sugar acids, sugar alcohols,
deoxy sugars, sugar phosphates, amino sugars and glycosides.
§ Sugar acids: Oxidation of aldo group of sugars produces aldonic acids.
For example, oxidation of glucose produces gluconic and oxidation of
terminal alcohol group (–OH sixth carbon atom) of glucose produces
glucuronic acid or uronic acid. Uronic acids are components of
mucopolysaccharides and required for detoxification. Ketoses are not
easily oxidized. Vitamin C or ascorbic acid is also sugar acid.
§ Sugar alcohols: Reduction of aldose and keto groups of sugar produces
polyhydroxy alcohols or polyols. These polyols are intermediates of
metabolic reactions. Other sugar alcohols are glycerol and inositol. The
alcohols formed from glucose, galactose and fructose are sorbitol,
galactitol and sorbitol, respectively.
§ Deoxy sugars: Those sugars in which oxygen of a hydroxyl group is
removed leaving hydrogen. Deoxyribose is an example. It is present in
nucleic acids. Fucose is another deoxy sugar present in blood group
substances.
 Derivatives of monosaccharides

Oxidation and reduction products of glucose

§ Sugar phosphates:Breakdown of sugar in animals involves formation of
sugar phosphates. Glucose-6-phosphate is an example for a sugar
phosphate.
§ Aminosugars: Those sugars in which an amino group is substituted for a
hydroxyl group. D-glucosamine is an example for an amino sugar. Amino
sugars are components of mucopolysaccharides, and antibiotics.
§ Glycosides: Are of two types:
§ O-glycosides. When hydroxyl group on anomeric carbon of a sugar reacts with an
alcohol (sugar) O-glycoside is formed. O-glycosidic linkage is present
in disaccharides and polysaccharides. So, disaccharides, oligosaccharides and
polysaccharides are O-glycosides.
§ N-glycosides. N-Glycoside is formed when hydroxyl group on anomeric carbon
of sugar reacts with an amine. N-glycosidic linkage is present in nucleotides, RNA
and DNA. So, nucleotides, RNA and DNA are examples for N-glycosides.