Carbohydrates
Introduction to General, Organic, and Biochemistry, 11th Edition by
Bettelheim, Brown, Campbell, Farrell, Torres
Organic Chemistry, 11th Edition by Solomons et.al.
Olivert M. Sitoy, M.Sc., R.Ch.
Chemistry Department
College of Arts and Sciences
Xavier University – Ateneo de Cagayan
Carbohydrates
Carbohydrate: Polyhydroxyaldehyde or polyhydroxyketone, or
compounds that produces such substances upon hydrolysis.
• The most abundant class of bioorganic molecules on earth
• Produced by the photosynthetic activity of the green plants
• Also referred as saccharides due to the sweet taste of
carbohydrates (sachharum, Latin: sugar)
• Storehouse of chemical energy (glucose, starch, glycogen)
• Supportive structural components in plants and some animals
(cellulose, chitin)
• Form part of the structural framework of DNA & RNA
• Carbohydrate “markers” on cell surfaces play key roles in cell-cell
recognition process
Carbohydrates
Carbohydrate: Polyhydroxyaldehyde or polyhydroxyketone, or
compounds that produces such substances upon hydrolysis.
• Monosaccharide: Single (1) polyhydroxyaldehyde or
polyhydroxyketone (e.g., Glucose and Fructose)
• Disaccharide: Two (2) monosaccharide units connected by
covalent bond (e.g., Sucrose and Lactose)
• Oligosaccharide: 2-10 monosaccharide units connected by
covalent bond (e.g., raffinose and stachyose)
• Polysaccharide: tens of thousands of monosaccharide units
connected by covalent bond (e.g., chitin and cellulose)
• Hybrid Carbohydrates: Carbohydrates with other biomolecules
• Derived Carbohydrates: modified carbohydrates through
reactions (e.g., sorbitol)
Monosaccharides
Monosaccharide: a carbohydrate that cannot be hydrolyzed to a
simpler carbohydrate.
• Monosaccharides have a general formula of CnH2nOn or Cn(H2O)n
where n varies from 3 to 8.
• Aldose: a monosaccharide containing an aldehyde group.
• Ketose: a monosaccharide containing a ketone group.
Monosaccharides
Monosaccharide: a carbohydrate that cannot be hydrolyzed to a
simpler carbohydrate.
• Monosaccharides have a general formula of CnH2nOn or Cn(H2O)n
where n varies from 3 to 8.
• Monosaccharides can be classified by their number of carbon
atoms
Name Formula Name Formula
Triose C3H6O3 Hexose C6H12O6
Tetrose C4H8O4 Heptose C7H14O7
Pentose C5H10O5 Octose C8H16O8
Monosaccharides
Problem: Classify the following monosaccharides according to both the
number of carbon atoms and the type of carbonyl group present.
Aldopentose Ketohexose Aldohexose Ketohexose
Monosaccharides
Glyceraldehyde: A simplest aldotriose with a stereocenter and exist as
a pair of enantiomer.
Monosaccharides
Fischer Projection: Two dimensional representation for showing the
configuration of tetrahedral stereocenters.
• Horizontal Lines: Bonds projecting forward
• Vertical Lines: Bonds projecting to the rear
• Stereocenter: the only one on the plane
Monosaccharides
Emil Fischer: Arbitrary assignments of D- and L- to the enantiomers of
glyceraldehyde (1891).
• D-monosaccharide: The –OH on its penultimate carbon is on the
right in a Fischer projection
• L-monosaccharide: The –OH on its penultimate carbon is on the
left in a Fischer projection
Important Monosaccharides
• The most common D-tetroses and D-pentoses are:
D-Erythrose D-Threose D-Ribose 2-Deoxy-D-Ribose
Ribose and Deoxyribose – present as
intermediates in metabolic pathway and are
important building blocks of RNA and DNA
Important Monosaccharides
• The most common D-hexoses are:
D-Glucose D-Fructose D-Galactose D-Mannose
5% (m/v) solution is used Found in bacteria, fungi
as IV source of and plants. Has no
nourishment for patients physiological relevance
Biologically Important Monosaccharides
Glucose
• Most abundant in nature
• Nutritionally most
important
• Grape fruit good source of
glucose (20-30% by mass)
– also named as grape
sugar, dextrose and blood
sugar (70-100mg/100 mL
of blood)
• Six membered cyclic form
Biologically Important Monosaccharides
Fructose
• Ketohexose
• Sweetest of all sugars; the
fruit sugar
• Found in many fruits and
in honey
• Good dietary sugar – due
to higher sweetness
• Five membered cyclic form
Biologically Important Monosaccharides
Galactose
• A component of milk sugar
• Synthesized in human
• Also called brain sugar –
part of the brain and nerve
tissue
• Used to differentiate
between blood types
• Six membered cyclic form
• Galactosemia – genetic
deficiency in infants
Biologically Important Monosaccharides
Ribose
• Part of RNA (Ribonucleic
Acid)
• Part of ATP (Adenosine
Triphosphate)
• Part of DNA
(Deoxyribonucleic Acid)
• Five membered cyclic form
Amino Sugars
Amino Sugars: Carbohydrates that contains –NH2 (-amino) group
instead of an –OH (-hydroxyl) group.
• Only three amino sugars are common in nature: D-Glucosamine,
D-Mannosamine, D- Galactosamine.
• In naturally occurring amino sugars, the carbon 2 hydroxyl group
is replaced by an amino group
Characteristic Reactions of Aldehydes and Ketones
Addition of Alcohols: Formation of Hemiacetal
• Hemiacetals are generally unstable except in cyclic hemiacetal
from.
Cyclic Forms of Monosaccharides (Haworth Projection)
D-Glucose forms these cyclic monosaccharides
All –OH on the left are
oriented UP, and all –OH on
the right are oriented DOWN
Glucose
(Plane Projection formula)
Cyclic Forms of Monosaccharides (Haworth Projection)
D-Glucose forms these cyclic monosaccharides
Counterclockwise
rotation of the
groups attached
to C5
Cyclic Forms of Monosaccharides (Haworth Projection)
D-Glucose forms these cyclic monosaccharides
α-D-Glucose β-D-Glucose
(The –OH in this form is (The –OH in this form is
oriented DOWN) oriented UP)
Cyclic Forms of Monosaccharides (Haworth Projection)
• The new carbon stereocenter
created in forming the cyclic
structure is called an anomeric
carbon.
• Stereoisomers that differ in
configuration only at the Anomeric Carbons
anomeric carbon are called
anomers.
• The anomeric carbon of an
aldose is C1; that of the most
common ketoses is C2.
Cyclic Forms of Monosaccharides (Haworth Projection)
• The new carbon stereocenter
created in forming the cyclic
structure is called an anomeric
carbon.
• Stereoisomers that differ in
configuration only at the Anomeric Carbons
anomeric carbon are called
anomers.
• The anomeric carbon of an
aldose is C1; that of the most
common ketoses is C2.
Cyclic Forms of Monosaccharides (Haworth Projection)
• β means that –OH on the
anomeric carbon is on the same
side of the ring as the terminal
CH2OH
• α means that –OH on the
anomeric carbon is on the Anomeric Carbons
opposite side of the ring as the
terminal CH2OH
• Six-membered hemiacetal ring is
called pyranose, and five-
membered ring is called
furanose
Cyclic Forms of Monosaccharides (Haworth Projection)
• β means that –OH on the
anomeric carbon is on the same
side of the ring as the terminal
CH2OH
• α means that –OH on the
anomeric carbon is on the
opposite side of the ring as the
terminal CH2OH
• Six-membered hemiacetal ring is
called pyranose, and five-
membered ring is called
furanose
Cyclic Forms of Monosaccharides (Haworth Projection)
• Aldopentoses also form cyclic hemiacetals.
• The most prevalent forms of D-ribose and other pentoses in the
biological world are furanoses.
• The prefix “deoxy” means “without oxygen”
Cyclic Forms of Monosaccharides (Haworth Projection)
• D-Fructose (2-ketohexose) also forms a five-membered cyclic
hemiacetal
Cyclic Forms of Monosaccharides (Chair Conformation)
• For pyranoses, the six-membered ring is more accurately
represented as a chair conformation
Cyclic Forms of Monosaccharides (Mutarotation)
• Mutarotation: Change in specific rotation that accompanies the
equilibrium of α- and β-anomers in aqueous solution
Physical Properties of Monosaccharides
• Monosaccharides are colorless crystalline solids, very soluble in
water, but only slightly soluble in ethanol.
Characteristic Reactions of Monosaccharides
Formation of Glycosides: Reaction with alcohols
• Monosaccharides in cyclic hemiacetal conformation reacts with
alcohol to form acetals
Characteristic Reactions of Monosaccharides
Formation of Glycosides: Reaction with alcohols
• Cyclic acetal from monosaccharide is called Glycoside.
• Bond between anomeric carbon to the –OR group is called
glycosidic bond.
• Mutarotation is not possible.
• Glycosides are stable in water and aqueous base
• Glycosides can be hydrolyzed in aqueous acid to an alcohol and a
monosaccharide.
Characteristic Reactions of Monosaccharides
Formation of Alditols: Reduction of Monosaccharides
• Carbonyl group of monosaccharides are reduced to hydroxyl
group using reducing agents (e.g., NaBH4, and H2 with transition
metal catalyst)
Characteristic Reactions of Monosaccharides
Formation of Alditols: Reduction of Monosaccharides
• Sorbitol: found in berries, cherries, plums, pears, apples,
seaweed, and algae. 60% percent as sweet as sucrose and is
used as sugar substitute.
• Three alditols also common in biological world.
Characteristic Reactions of Monosaccharides
Formation of Aldonic Acid: Oxidation of Monosaccharides
• Aldehyde group of aldoses is oxidized under basic condition
• Carbohydrates that reacts with an oxidizing agent to form
aldonic acid is classified as reducing sugar.
Characteristic Reactions of Monosaccharides
Formation of Uronic Acid: Oxidation of Monosaccharides
• Enzyme catalyzed oxidation of primary alcohols at C6 of hexoses.
Characteristic Reactions of Monosaccharides
Formation of Uronic Acid: Oxidation of Monosaccharides
• Glucoronic acid is widely distributed in plants and animal world.
Characteristic Reactions of Monosaccharides
Formation of Phosphate Esters: Phosphoric acid reacts with
monosaccharides
• Phosphate esters are intermediates in the metabolism of
monosaccharides
Disaccharides
Sucrose
• Composed of
Glucose and
Fructose
• Known as Table
Sugar.
• The most abundant
disaccharide in the
biological world
• Obtained from sugar
cane and sugar
beets
• Non-reducing sugar.
Disaccharides
Lactose
• Composed of
Glucose and
Galactose
• Principal sugar
in Milk
• 5-8% in Human
milk
• 4-6% in Cow
milk
• Reducing Sugar
Disaccharides
Maltose
• Composed of Glucose
and Glucose
• Present in Malt, Juice
of sprouted barley
and other cereal
grains
• Reducing Sugar
Cellobiose
• Same with maltose
but connected by β-
Glucosidic linkage
Disaccharides
Maltose
• Composed of Glucose
and Glucose
• Present in Malt, Juice
of sprouted barley
and other cereal
grains
• Reducing Sugar
Cellobiose
• Same with maltose
but connected by β-
Glucosidic linkage
Polysaccharides
Starch: Polymer of Glucose
• Can be separated into Amylopectin and Amylose
Polysaccharides
Starch: Polymer of Glucose
• Amylose: unbranched chains up to 4000 D-Glucose joined by α-
1,4-glycosidic bond
• Amylopectin: unbranched chains up to 10000 D-Glucose joined
by α-1,4-glycosidic bond; at branching points, new chains of
24to30 units of glucose by 1,6-glycosic bond
Polysaccharides
Glycogen: Polymer of Glucose
• Energy-reserve carbohydrate of animals
• Branched polysaccharide of approximately 106 glucose units
joined by α-1,4- and α-1,6-glycosidic bond
• Well-nourished adult human has about 350 g of glycogen in liver
and muscle.
Polysaccharides
Cellulose: Polymer of Glucose
• Average molecular weight of 400,000 g/mol; approximately
2200 glucose units per molecule
Polysaccharides
Cellulose: Polymer of Glucose
• Cellulose molecules act like stiff rods and align themselves side
by side into well-organized water-insoluble fibers in which –OH
groups form numerous intermolecular hydrogen bonds
• This arrangement of parallel chains in bundles give cellulose
fibers their high mechanical strength
Polysaccharides
Cellulose: Polymer of Glucose
• Human and other animals cannot digest cellulose due to
absence of β-glucosidase (The enzyme that degrades or breaks
down cellulose into glucose)
• Humans only have α-glucosidase that degrades/breakdowns
starch and glycogen
• Bacteria and microorganism has β-glucosidase
• Termites have such bacteria in their intestines and use wood as
their principal food
• Ruminants (cud chewing animals) and horse can also digest
grasses and hay.
Polysaccharides
Starch and Cellulose: Polymer of Glucose
Acidic Polysaccharides
Acidic Polysaccharides: Polymer containing sugar acids
• Group of polysaccharides that contain carboxyl groups and/or
sulfuric ester groups, and play important role in the structure
and function of connective tissues.
• No single general type of connective tissue.
• A large number of highly specialized form exist (e.g., cartilage,
bone, synovial fluid, skin, tendons, blood vessels, intervertebral
disk and cornea)
• Most connective tissues are made up of collagen, a structural
protein, in combination with a variety of acidic polysaccharides
Acidic Polysaccharides
Hyaluronic Acid: Polymer of Glucoronic Acid and N-Acetylglucosamine
• Contains from 300 to 100000 repeating units
• Most abundant in embryonic tissued and in specialized
connective tissues (e.g., synovial fluid lubricant of joints in the
body, and vitreous of the eye)
Acidic Polysaccharides
Heparin: Polymer of sulfated Glucoronic Acid and Glucosamine
Acidic Polysaccharides
Heparin: Polymer of sulfated Glucoronic Acid and Glucosamine
• Anticoagulant in blood (inhibits blood clot formation)
• Used in open-heart surgery
• Synthesized and stored in mast cells of various tissues (e.g., liver,
lungs and gut).
• Binds with antithrombin III, a plasma protein, involved in
terminating the clotting process.
