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CARBOHYDRATES

Introduction
• Carbohydrates are carbon compounds that
contain large quantities of hydroxyl (-OH) groups
• The simplest carbohydrates also contain either an
aldehyde moiety (these are termed
polyhydroxyaldehydes) or a ketone moiety
(polyhydroxyketones).
• Thus carbohydrates are aldehyde or ketone
compounds with multiple hydroxyl groups
• All carbohydrates can be classified as either
monosaccharides, oligosaccharides or
polysaccharides
• Condensation products of two to ten
monosaccharide units, linked by glycosidic bonds,
make up an oligosaccharide.
• Polysaccharides are much larger, containing
hundreds of monosaccharide units.
• The presence of the hydroxyl groups allows
carbohydrates to interact with the aqueous
environment and to participate in hydrogen
bonding, both within and between chains.
• Derivatives of the carbohydrates can contain
nitrogens, phosphates and sulfur compounds.
• Carbohydrates also can combine with lipids to
form glycolipids or with proteins to form
glycoproteins.
Occurance of carbohdrates

in plants in animals
- First product of photo- - blood sugar : D-glucose
synthesis - milk sugar: lactose
- Stored in foods as starch, - stored as glycogen
inulin and hemicelluloses - essential components of
nucleic acids: ribose
- Supporting tissue of
- plants: cellulose
- Degradation products:
gums and mucilages
- Miscellaneous : pectins,
glucosides
Quick Structural
CARBOHYDRATES energy support

MONOSACCHARIDES
(simple sugars)
DISACCHARIDES POLYSACCHARIDES

fructose glucose galactose sucrose maltose lactose starch glycogen cellulose chitin

fruits plants milk sugar beets grains milk stored stored forms cell insects
sugar cane glucose glucose walls in
İn plants İn animals plants

Table sugar
Functions
• First, carbohydrates serve as energy stores, fuels,
and metabolic intermediates.
• Second, ribose and deoxyribose sugars form part
of the structural framework of RNA and DNA.
• Third, polysaccharides are structural elements in
the cell walls of bacteria and plants.
• Fourth, carbohydrates participate in biological
transport, cell-cell recognition, activation of
growth factors, modulation of the immune
system
• Fifth, carbohydrates are associated with other
entities such as glycosides, vitamins and
antibiotics)
Nomenclature
• The predominant carbohydrates encountered in the
body are structurally related to the aldotriose
glyceraldehyde and to the ketotriose
dihydroxyacetone.
• All carbohydrates contain at least one asymmetrical
(chiral) carbon and are, therefore, optically active.
• In addition, carbohydrates can exist in either of two
conformations, as determined by the orientation of the
hydroxyl group about the asymmetric carbon farthest
from the carbonyl.
• With a few exceptions, those carbohydrates that are of
physiological significance exist in the D-conformation.
– The mirror-image conformations, called enantiomers, are
in the L-conformation.
Monosaccharides
• The monosaccharides commonly found in humans are classified according
to the number of carbons they contain in their backbone structures. The
major monosaccharides contain four to six carbon atoms.

# Carbons Category Name Relevant examples

3 Triose Glyceraldehyde, Dihydroxyacetone

4 T etrose Erythrose

5 Pentose Ribose, Ribulose, Xylulose

6 Hexose Glucose, Galactose, Mannose, Fructose

7 Heptose Sedoheptulose

9 Nonose Neuraminic acid also called sialic acid


Properties
• Differences in structures of sugars are
responsible for variations in properties

– Physical
– Crystalline form; solubility; rotatory power
– Chemical
– Reactions (oxidations, reductions, condensations)
– Physiological
– Nutritive value (human, bacterial); sweetness; absorption
• The aldehyde and ketone moieties of the
carbohydrates with five and six carbons will
spontaneously react with alcohol groups present
in neighbouring carbons to produce
intramolecular hemiacetals or hemiketals,
respectively.
– This results in the formation of five- or six-membered
rings.
• Because the five-membered ring structure
resembles the organic molecule furan, derivatives
with this structure are termed furanoses.
• Those with six-membered rings resemble the
organic molecule pyran and are termed
pyranoses.
Such structures can be depicted by either Fischer or Haworth style diagrams.

Cyclic Fischer Projection of α-D-Glucose Haworth Projection of α-D-Glucose


• The rings can open and re-close, allowing rotation to
occur about the carbon bearing the reactive carbonyl
yielding two distinct configurations (α and β) of the
hemiacetals and hemiketals.
• The carbon about which this rotation occurs is the
anomeric carbon and the two forms are termed
anomers.
• Carbohydrates can change spontaneously between the
α and β configurations-- a process known as
mutarotation.
• When drawn in the Fischer projection, the α
configuration places the hydroxyl attached to the
anomeric carbon to the right, towards the ring.
• When drawn in the Haworth projection, the α
configuration places the hydroxyl downward.
• Simple sugars also differ in the positions
of hydroxyl groups and hydrogen around
the ring

• Causes variations in:


1. Solubility
2. Sweetness
3. Rates of fermentation
Disaccharides
• Covalent bonds between the anomeric
hydroxyl of a cyclic sugar and the hydroxyl of a
second sugar (or another alcohol containing
compound) are termed glycosidic bonds, and
the resultant molecules are glycosides.
• The linkage of two monosaccharides to form
disaccharides involves a glycosidic bond.
• Several physiogically important disaccharides
are sucrose, lactose and maltose
Reducing sugars

• Reactive aldehyde and ketone groups are


not involved in linking, they are free
to react and reduce Fehling’s solution.

• Maltose: reducing sugar


• Sucrose: nonreducing sugar
Sucrose
Prevalent in sugar cane and sugar beets, is composed
of glucose and fructose through an α-(1,2) glycosidic
bond.

Sucrose
Lactose
is found exclusively in the milk of mammals and
consists of galactose and glucose in a β-(1,4) glycosidic
bond

Lactose
Maltose
the major degradation product of starch, is composed of
2 glucose monomers in an α-(1,4) glycosidic bond.
Oligosaccharides
• Trisaccharide: raffinose (glucose, galactose
and fructose)
• Tetrasaccharide: stachyose (2 galactoses,
glucose and fructose)
• Pentasaccharide: verbascose (3 galactoses,
glucose and fructose)
• Hexasaccharide: ajugose (4 galactoses, glucose
and fructose)
Oligosaccharides occur widely as components of
antibiotics derived from various sources
Polysaccharides
• Most of the carbohydrates found in nature occur
in the form of high molecular weight polymers
called polysaccharides.
• The monomeric building blocks used to generate
polysaccharides can be varied; in all cases,
however, the predominant monosaccharide
found in polysaccharides is D-glucose.
• When polysaccharides are composed of a single
monosaccharide building block, they are termed
homopolysaccharides.
• Polysaccharides composed of more than one type
of monosaccharide are termed
heteropolysaccharides.
Glycogen
• Glycogen is the major form of stored carbohydrate in
animals.
• This crucial molecule is a homopolymer of glucose in
α-(1,4) linkage; it is also highly branched, with α-(1,6)
branch linkages occurring every 8-10 residues.
• Glycogen is a very compact structure that results from
the coiling of the polymer chains.
• This compactness allows large amounts of carbon
energy to be stored in a small volume, with little effect
on cellular osmolarity
• Complete hydrolysis yields glucose
• Glycogen and iodine gives a red-violet color
Starch
• Starch is the major form of stored
carbohydrate in plant cells.
• Its structure is identical to glycogen, except
for a much lower degree of branching (about
every 20-30 residues).
• Unbranched starch is called amylose;
branched starch is called amylopectin
Amylose and amylopectin are the 2 forms of starch. Amylopectin
is a highly branched structure, with branches occurring every 12
to 30 residues
•Suspensions of amylose
in water adopt a helical
conformation

•Iodine (I2) can insert in


the middle of the amylose
helix to give a blue color
that is characteristic and
diagnostic for starch
Cellulose
• Cellulose, the other major polysaccharide of glucose found
in plants, serves a structural rather than a nutritional role.
• Cellulose is one of the most abundant organic compounds
in the biosphere.
• It is an unbranched polymer of glucose residues joined by
β-1,4 linkages.
• The β configuration allows cellulose to form very long,
straight chains.
• Fibrils are formed by parallel chains that interact with one
another through hydrogen bonds.
• The α-1,4 linkages in glycogen and starch produce a very
different molecular architecture from that of cellulose.
(in starch)

(in cellulose)
Cellulose
• Yields glucose upon complete hydrolysis
• Partial hydrolysis yields cellobiose
• Most abundant of all carbohydrates
• Cotton flax: 97-99% cellulose
• Wood: ~ 50% cellulose
• Gives no color with iodine
• Held together with lignin in woody plant tissues
Chitin
• Chitin is the second most abundant
carbohydrate polymer
• Present in the cell wall of fungi and in the
exoskeletons of crustaceans, insects and
spiders
• Chitin is used commercially in coatings
(extends the shelf life of fruits and meats)
Linear structures of cellulose and chitin
(2 most abundant polysaccharides)
Inulin
• β-(1,2) linked fructofuranoses
• Linear only; no branching
• Lower molecular weight than starch
• Colors yellow with iodine
• Hydrolysis yields fructose
• Sources include onions, garlic etc
• Used as diagnostic agent for the evaluation of
glomerular filtration rate (renal function test)
Dextrans
• Products of the reaction of glucose and the enzyme
transglucosidase from Leuconostoc mesenteroides
• Contains α (1,4), α (1,6) and α (1,3) linkages
• MW: 40,000; 70,000; 75,000
• Used as plasma extenders (treatment of shock)
• Also used as molecular sieves to separate proteins
and other large molecules (gel filtration
chromatography)
• Components of dental plaques
Dextrins
• Produced by the partial hydrolysis of starch
along with maltose and glucose
• Dextrins are often referred to as either
amylodextrins, erythrodextrins or
achrodextrins
• Used as mucilages (glues)
• Also used in infant formulas (prevent the
curdling of milk in baby’s stomach)
Glycoconjugates
• These are carbohydrates with protein or lipid
conjugates
• They include
– Peptidoglycan
– Proteoglycan
– Glycolipids
– Glycoprotein
Glycosaminoglycans (GAGS)
• They are the polysaccharide chains of proteoglycans
• They are linked to the protein core via a serine or threonine
(O-linked)
• The chains are linear (unbranched)
• The glycosaminoglycan chains are long (over 100
monosaccharides)
• Glycosaminoglycans are unbranched polysaccharide chains of
repeating disaccharide units (N-acetylgalactosamine (GalNAc)
or N-acetylglucosamine (GlcNAc) and a uronic acid such as
glucuronate or iduronate)
GAGs of Physiological significance

• Involved in a variety of extracellular functions;

– Hyaluronic acid (lubricant in synovial joint)

– Dermatan sulphate (skin, blood vessels, heart

valves)

– Heparin & heparin sulphate (in blood clotting)

– Keratin sulphate (skin, cornea, bone, cartilage)


Glycosaminoglycans
•A characteristic of glycosaminoglycans is the presence
of acidic functionalities (carboxylate and/or sulfates)
Bacterial cell wall
• Provide strength and rigidity for the organism
• Consists of a polypeptide-polysaccharide known
as petidoglycan or murein
– Heteropolymer of alternating N-acetylglucosamine
and N-acetylmuramic acid in β-(1,4) glycosidic linkage
• Determines the Gram staining characteristic of
the bacteria
• Many antibiotics work by inhibiting normal
synthesis of peptidoglycan in bacteria causing
them to burst as a result of osmotic lysis
Structure of Peptidoglycan:
Structure of Peptidoglycan: Staphylococcus aureus (Gram
Escherichia coli (Gram -) +)
Gram stain morphology of bacteria
Gram Stain of E. coli Gram Stain of S. aureus
Glycoproteins
• Proteins with covalently bonded carbohydrate
• Found in almost all organisms
• The oligosaccharide content is usually
between 1 to 30%
• Sugars maybe neutral sugars, amino sugars,
uronic acids or neuramic acid
• The carbohydrate portions of glycoproteins
perform important biological functions
– Carry determinants of human ABO blood grouping
– Stabilize the protein conformations
– Are involved in immunoprotection (cytokines,
immunoglobulins)
– Are involved in cell-cell or cell-molecule
recognition events (host-parasite interactions)
– Are involved in blood clotting
ABO blood group antigens
• Blood group classifications depend on
differences in oligosaccharide structure
bonded to a protein called glycophorin and
lipids (glycosphingolipids) of RBC membranes
• It is the terminal sugar of the oligosaccharide
that distinguishes the different blood group
cells
• These minor differences in the sugars result in
the differences in compatibility of the blood
types
ABO Antigens
• Diseases associated with carbohydrate
metabolism include
– diabetes mellitus,
– galactosemia,
– glycogen storage diseases, and
– lactose intolerance.