Carbohydrate Chemistry
Auto-brewery syndrome or gut
fermentation syndrome
• condition in which ethanol is produced
through endogenous fermentation by fungi or
bacteria in the gastrointestinal (GI) system.
• Patients with auto-brewery syndrome present
with many of the signs and symptoms of
alcohol intoxication while denying an intake of
alcohol and often report a high-sugar, high-
carbohydrate diet.
The carbohydrates are widely distributed both in animal
and plant tissues.
Chemically, they contain elements carbon, hydrogen &
oxygen
Empirical formula of many simple carbohydrates is
[CH2O]n. Hence, the name “carbohydrate”, i.e.
hydrated carbon.
They are also called “saccharides”. In Greek,
saccharon means sugar.
Definition
Carbohydrates are aldehyde or ketone
derivatives of polyhydroxy alcohols or as
compounds that yield these derivatives on
hydrolysis.
Classification of Carbohydrate
1. Monosaccharides
2. Oligosaccharides
3. Polysaccharides.
Monosaccharides (Greek: Mono = one)
Monosaccharides are also called simple sugars.
The term sugar is applied to carbohydrates that
are soluble in water and sweet to taste.
They cannot be hydrolyzed into a simpler form.
They may be subdivided into two groups.
Oligosaccharides (Greek: oligo = few)
Short chain of monosaccharide units (2 to 10 units),
joined together by glycosidic bond
On hydrolysis, gives two to ten molecules of simple
sugar (monosaccharide) units.
Oligosaccharides are subdivided into different groups
based on the number of monosaccharide units present
Polysaccharides (Greek: Poly = many) or Glycans
Polymers consisting of hundreds or thousands of
monosaccharide units.
They are also called glycans or complex carbohydrates.
They may be either linear, (e.g. cellulose) or branched,
(e.g. glycogen) in structure.
Polysaccharides have high molecular weight and are only
sparingly soluble in water.
They are not sweetish and do not exhibit any of the
properties of aldehyde or ketone group.
Functions of Carbohydrates
Source of energy for living beings, e.g. glucose
Storage form of energy, e.g. glycogen in animal tissue
and starch in plants
Serve as structural component, e.g. glycosaminoglycans
in human, cellulose in plants and chitin in insects
Non-digestible carbohydrates like cellulose, agar, gum
and pectin serve as dietary fibers.
Constituent of RNA and DNA, e.g. ribose and
deoxyribose sugar.
Carbohydrate play a role in lubrication, cellular
intercommunication and immunity.
Carbohydrates are also involved in detoxification, e.g.
glucuronic acid
Structure of Glucose
1. The straight chain structural formula
(Fisher projection)
2. Cyclic formula
(Ring structure or Haworth projection)
Monosaccharide in solution mainly present in
ring form.
In solution, the aldehyde group of glucose at
C-1 reacts with alcohol (OH) group of C-5 to
form six membered ring called
glucopyranose
The aldehyde group of glucose at C-1 reacts
with alcohol (OH) group of C-4 to form five
membered ring called glucofuranose.
In case of glucose, the six membered
glucopyranose is much more stable than the
glucofuranose ring.
In the case of fructose, the more stable form is
fructofuranose
Isomerism
The compounds possessing identical
chemical (molecular) formula but different
structures are referred to as isomers.
Important types of isomerism
1. Aldose- ketose isomerism
2. D and L isomerism
3. Optical isomerism
4. Epimerism
5. Anomerism (α and β Anomerism)
Aldose-Ketose isomerism
D and L Isomerism
D and L isomerism depends on the orientation of
the H and OH groups around the asymmetric
carbon atom adjacent to the terminal primary
alcohol carbon.
Carbon atom number 5 in glucose determines
whether the sugar belongs to D or L isomer.
When OH group on this carbon atom is on the
right, it belongs to D-series, when it is on the
left; it is the member of the L-series.
The structures of D and L-glucose based on the
reference monosaccharide, D and L
glyceraldehyde, a three carbon sugar.
D and L isomers (enantiomeric pairs) of
glyceraldehyde
D and L isomers of
glucose.
Most of the monosaccharides in the living beings
belong to the D-series. (unlike amino acids
which are L isomers).
D and L isomers are mirror images of each other.
These two forms are called enantiomers.
Optical Isomerism
Optical activity is the capacity of a substance to
rotate the plane polarized light passing through it.
When a beam of plane-polarized light is
passed through a solution of an optical isomer,
it will be rotated either to the right and is said
to be dextrorotatory (d) or (+) or to the left and
is said to be, levorotatory (l) or (-).
In solution, glucose is dextrorotatory that
is why glucose solutions sometimes
known as dextrose.)
d-, and l- nomenclature is unrelated to D-
and L-isomerism. This nomenclature is
obsolete.
When equal amount of (+) and (- ) isomers are present,
the resulting mixture has no optical activity such a
mixture is said to be a racemic mixture.
Epimerism
When two monosaccharides differ from each other in
their configuration around a single asymmetric
carbon (other than anomeric carbon) atom, they are
referred to as epimers of each other.
Epimers of glucose.
Anomerism
Carbon-1 of glucose in the open chain form
becomes an asymmetric carbon in the ring form
and two ring structures can be formed. These are:
• α -D-glucose
• β -D-glucose
Generation of new asymmetric carbon atom at
C1
α and β Anomers
The designation α means that the hydroxyl
group attached to C-1 is below the plane of
the ring, β means that it is above the plane
of the ring.
The C-1 carbon is called the anomeric
carbon atom and so, α and β forms are
anomers.
Glycoside Formation
When the hydroxyl group on the anomeric
carbon of a monosaccharides reacts with OH or
NH group of another compound (it may or may
not be a monosaccharide) glycosides are formed.
The N type of glycoside bonds
Therapeutic Importance of Glycosides
Found in many drugs, e.g. in antibiotic
streptomycin.
Cardiac glycosides such as Ouabain and
digoxin increase heart muscle contraction and
are used for treatment of congestive heart
failure.
Daunorubicin is used to treat leukaemia.
Doxirubicin is used to treat cancers.
Oligosaccharides
Oligosaccharides consist of short chains of
monosaccharide units (2 to 10 units)
Joined together by glycosidic linkages
Among oligosaccharides disaccharide is
most abundant
The disaccharides which have two monosaccharide units
are the most abundant in nature.
Oligosaccharides with more than three subunits are
usually found in glycoproteins; such as blood group
antigens.
DISACCHARIDES
Disaccharides consist of two monosaccharide units.
They are crystalline, water soluble and sweet to
taste.
They are subclassified on the basis of the presence
or absence of free reducing group.
In disaccharides the glycosidic linkage may be
either α or β depending on the configuration of
the atom attached to the anomeric carbon of the
sugar
Polysaccharides (Glycans)
Composed of ten or more monosaccharide units
or their derivatives.
Monosaccharide units are joined together by
glycosidic bond
Colloidal in nature.
Polysaccharides Subclassified into
1. Homopolysaccharide
2. Heteropolysaccharide
Classification of polysaccharide.
Homopolysaccharides or Homoglycans
Starch
It is the storage form of glucose in plants.
Starch is composed of two constituents
,amylose and amylopectin.
Amylose
Amylose is a linear polymer of D-glucose units
joined by α-1, 4 glycosidic linkages
Amylopectin
Amylopectin is branched structure with α-1, 4 and
α-1, 6 glycosidic linkages
Amylose, glucose units joined by α-1,4 linkages
Structure of
amylopectin
Amylopectin, glucose units joined by α-1,4 and α-1,6
linkages
Glycogen (Animal Starch)
Glycogen is the major storage form of
carbohydrate in animals, found mostly in liver
and muscle. It is often called animal starch.
Functions
• The function of muscle glycogen is to act as a
readily available source of glucose for energy
within muscle itself
• Liver glycogen is concerned with storage and
main- tenance of the blood glucose.
Diagrammatic representation of glycogen
molecule
Cellulose
Constituent of cell wall of plants.
Unbranched polymer of glucose linked by β-(1, 4)
glycosidic linkages and not α-(1,4)
Humans lack an enzyme cellulase that can
hydro- lyzeβ-(1, 4) glycosidic linkages of
poly- saccharides,cellulose cannot be digested and
absorbed
Structure of cellulose
Importance Of Cellulose
Cellulose is a component of fibre in the diet
High fibre diet is associated with reduced
incidence of
cardiovascular disease
colon cancer
diabetes
It increases bulk of stool, aids intestinal motility
and prevents constipation.
Inulin
Inulin is a polymer of D-Fructose (Fructosans)
linked together by β-(1 → 2) glycosidic
linkage.
It occurs in the tubers of some plants, e.g.
chicory, bulb of onion and garlic.
Inulin is not hydrolyzed by α-amylase but
is hydrolyzed by inulinase, which is not
present in the humans and so it is not
utilized as food.
Clinical importance of Inulin
Inulin has clinical importance as it is used in the
studies of glomerular filtration rates (kidney
function test).
Glycosaminoglycans (GAGs) or Mucopolysaccharides
Glycosaminoglycans were first isolated from
mucin which led to the original naming of these
compounds as mucopolysaccharide.
Structure of GAG
Unbranched, made up of repeating disaccharides :
(amino sugar : uronic acid)n
Amino sugar : D-glucosamine or
D-galactosamine
Uronic acid : Glucuronic acid or its epimer
Iduronic acid.
Sugar acids produced by oxidation of glucose
Polymer of amino sugar - Uronic acid is
attached covalently to proteins called core protein
to form proteoglycans.
A resulting structure resembles a “bottle brush”.
Bottle brush structure of proteoglycan
monomer
The proteoglycan monomer associates with a
molecule of hyaluronic acid to form proteoglycan
aggregates.
The association is not covalent, but occurs through
ionic interaction between core protein and the
hyaluronic acid.
The association is stabilized by additional small
proteins called link proteins.
Proteoglycan aggregate.
Occurrence Of Gags
Synovial fluid of joints
Vitreous humour of the eye
Arterial walls
Bones and
Cartilage.
Different types of GAGs
Hyaluronic Acid
Condroitin sulfate
Keratan sulfate
Dermatan sulfate
Heparin
Heparin sulfate
With the exception of hyaluronic acid, all the
GAGs contain sulfate group.
The amount of carbohydrates in proteoglycans
is upto 95 percent of its weight
Different types of GAGs differ from each other in:
Uronic acid composition
Amino sugar composition
Linkage between amino sugar and uronic acid
Chain length of the disaccharide polymer.
Presence or, absence of sulfate groups
Nature of core protein to which they are attached.
Their tissue and subcellular distribution and their
functions
Functions Of GAGs
Structural component. They are major components
of the extracellular matrix or ground substance.
Have special ability to bind large amounts of water,
producing a gel like matrix which functions as a
cushion against mechanical shocks
Negatively charged glycosaminoglycans chain repel
each other, and proteoglycans occupy a very large
space and act as “molecular sieves”, determining
which substances enter and leave cells.
They also give elasticity (resilience) to cartilage,
permitting compression and reexpansion.
They lubricate joints.
Strike a Note
Glycosaminoglycans were first isolated from
mucin which led to original name as
mucopolysaccharide.
One component is always an amino sugar hence
the name glycosaminoglycans.
Proteoglycans consist of up to 95% carbohydrate
by weight.
Except for hyaluronic acid, the
glycosaminoglycans are linked to protein.
Glycosaminoglycan not covalently linked to
protein is hyaluronic acid.
Glycosaminoglycan with no Uronic acid is
keratan sulfate.
Glycosaminoglycan with not sulfate group is
hyaluronic acid.
Glycosaminoglycans are generally
extracellular, only intracellular
glycosaminoglycan is heparin.
GLYCOPROTEIN
Proteins to which oligosaccharides are covalently
attached.
Glycoproteins contain much shorter carbohydrate chain
than proteoglycans.
These oligosaccharide chains are often branched instead
of linear and may or may not be negatively charged as
proteoglycans.
Functions Of Glycoproteins
Almost all the plasma proteins of humans are
glycoproteins, except albumin.
Many integral membrane proteins are glycoproteins.
Most proteins, such as antibodies, hormones and
coagulation factors are glycoproteins
Serve as lubricant and protective agent
It also serve to transport molecules.
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