UNIT 2

CARBOHYDRATE

DMT 20053 – FOOD CHEMISTRY

 OBJECTIVES
• At the end of the session, students should be able to:
– Explain the function, sources and composition of
carbohydrate in food.
– Classify carbohydrate into monosaccharide, disaccharide and
polysaccharide.
– Explain the structure and reaction of monosaccharide and
disaccharides.
– Clarify the basic chemical reaction for detection and tests.
– Explain briefly properties and structural class of
polysaccharides.
– Explain the changes during processing.
– Explain the methods and instruments involved in
carbohydrate determination.
DMT 20053 – FOOD CHEMISTRY
 INTRODUCTION
• The term is derived from France: hydrate de carbone
• ‘Carbohydrate’ is a combination of:
– “Carbo” means elements of Carbon
– “Hydrate” means Water
• Comes from a process called ‘photosyntesis’

DMT 20053 – FOOD CHEMISTRY

 INTRODUCTION
• C:H:O (1:2:1)
• The most abundant organic
molecules in nature:
– Major component of plant
tissue
– Comprise up to 70% or more of
dry matter of forages
– Make up less than 1% of the
weight of animals

DMT 20053 – FOOD CHEMISTRY

 SOURCES
• Animal products
– Minor (except lactose in
milk)
• Plants - major source
– Starch (storage of energy)
– Cellulose (structural)
– Sugar
– Gums

DMT 20053 – FOOD CHEMISTRY

 SOURCES
• Most carbohydrates are found naturally in bound
form rather than as simple sugars:
– Polysaccharides (starch, cellulose, inulin, gums)
– Glycoproteins and proteoglycans (hormones, blood group
substances, antibodies)
– Glycolipids (cerebrosides, gangliosides)
– Glycosides
– Mucopolysaccharides (hyaluronic acid)
– Nucleic acids
• Most plants contain different types of carbohydrates
than animals

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 FUNCTION
• Functions of carbohydrate:
– Sources of energy;
– Intermediates in the biosynthesis of other basic
biochemical entities (fats and proteins);
– Associated with other entities such as glycosides, vitamins
and antibiotics);
– Form structural tissues in plants and in microorganisms
(cellulose, lignin, murein);
– Participate in biological transport, cell-cell recognition,
activation of growth factors, modulation of the immune
system.

DMT 20053 – FOOD CHEMISTRY

 FUNCTION
• Functions of
carbohydrate
in foods:
– Fibre
– Gelling
agent
– Stabilizer
– Thickener
– Sweetener
– Fat replacer

DMT 20053 – FOOD CHEMISTRY

 COMPOSITION
• Carbohydrates are polyhydroxy (more hydroxyl
group –OH) aldehydes or ketones

Aldehyde Ketone

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 CLASSIFICATION
• Classified according to the number of sugar molecules:
– Monosaccharide (1 unit) : simple sugar with multiple OH
groups.
– Disaccharides (2 units) : 2 monosaccharides covalently linked
– Oligosaccharides (3 – 10 units) : a few monosaccharides
covalently linked
– Polysaccharides (greater than 10 units) : polymers consisting
of chains of monosaccharide or disaccharide units

I
(CH2O)n or H - C - OH
I
DMT 20053 – FOOD CHEMISTRY
 MONOSACCHARIDE
• Classified by:
– The number of carbon atoms: Sugars that
• 3-C triose contain four
• 4-C tetrose or more
carbons
• 5-C pentose Nutritionally exist
• 6-C hexose Important primarily in
cyclic form
– Contains aldeyde or ketone group:
• 1 group of aldehyde aldose
• 1 group of ketone ketose

DMT 20053 – FOOD CHEMISTRY

 MONOSACCHARIDE
Aldoses (e.g., glucose) have Ketoses (e.g., fructose) have
an aldehyde group at one a keto group, usually at C2.
end.

H O
C CH2OH

H C OH C O

HO C H HO C H

H C OH H C OH

H C OH H C OH

CH2OH CH2OH

D-glucose D-fructose

DMT 20053 – FOOD CHEMISTRY

 MONOSACCHARIDE
• Pentoses (5C)
– Xylose and arabinose
• Component in hemicellulose, glycoproteins
– Ribose
• Found in every living cell
• Found in compounds involved in metabolism:
– ATP/ADP
– Riboflavin
– DNA/RNA

DMT 20053 – FOOD CHEMISTRY

 MONOSACCHARIDE
H O

• Hexoses (6C) H
C

C OH

– Glucose HO C H

• Component of starch, cellulose, and glycogen H C OH

H C OH
• Major end-product of carbohydrate digestion in CH2OH
monogastrics D-glucose
• Primary form of sugar used for energy
CH2OH

C O
– Fructose HO C H

• 75% of sugars in honey H C OH

• Found in fruits and cane sugar H C OH

CH2OH

D-fructose

DMT 20053 – FOOD CHEMISTRY

 MONOSACCHARIDE
– Galactose – Mannnose
• Component of milk • Found after hydrolysis
sugar (lactose) of plant mannosans
• May be metabolized to and gums; legumes
glucose

Glucose, fructose, and galactose are among the most important

monosaccharides in living organisms
DMT 20053 – FOOD CHEMISTRY
 MONOSACCHARIDE
• D vs L CHO CHO
designation:
H C OH HO C H
– Based on the
configuration CH2OH CH2OH
about the single D-glyceraldehyde L-glyceraldehyde
asymmetric C in
glyceraldehyde. CHO CHO
– The lower H C OH HO C H
representations
are Fischer CH2OH CH2OH
Projections. D-glyceraldehyde L-glyceraldehyde

DMT 20053 – FOOD CHEMISTRY

 MONOSACCHARIDE
O H O H • Sugar
C C nomenclature:
– For sugars with
H – C – OH HO – C – H
more than one
HO – C – H H – C – OH chiral center, D or
H – C – OH HO – C – H L refers to the
asymmetric C
H – C – OH HO – C – H
farthest from the
CH2OH CH2OH aldehyde or keto
D-glucose L-glucose group.
– Most naturally
D & L sugars are mirror occurring sugars
images of one another are D isomers.

DMT 20053 – FOOD CHEMISTRY

 MONOSACCHARIDE
• Hemiacetal & hemiketal formation:
H H
An aldehyde can
react with an C O + R' OH R' O C OH
alcohol to form R R
a hemiacetal. aldehyde alcohol hemiacetal

A ketone can R R
react with an C O + "R OH "R O C OH
alcohol to form
R' R'
a hemiketal. ketone alcohol hemiketal

DMT 20053 – FOOD CHEMISTRY

 MONOSACCHARIDE
Pentoses and 1
CHO

hexoses can cyclize H

2
C OH

as the ketone or HO
3
C H D-glucose
(linear form)
aldehyde reacts H
4
C OH

with a distal OH. H

5
C OH

CH2OH
Glucose forms an 6 CH2OH
6

6 CH2OH
intra-molecular H
5 O H H
5 O OH
hemiacetal, as the 4
H
OH H 1 4
H
OH H 1

C1 aldehyde & C5 OH
3 2
OH OH
3 2
H

OH react, to form H OH H OH
-D-glucose -D-glucose
a 6-member
pyranose ring, These representations of the cyclic sugars
are called Haworth projections
named after pyran.
DMT 20053 – FOOD CHEMISTRY
 MONOSACCHARIDE
1
CH2OH

2C O

HO C H
1 CH2OH
3 HOH2C 6 O
H C OH HO
4 5 H 2

H C OH H 4 3 OH
5
OH H
6
CH2OH

D-fructose (linear) -D-fructofuranose

Fructose forms either

• a 6-member pyranose ring, by reaction of the C2 keto
group with the OH on C6, or
• a 5-member furanose ring, by reaction of the C2 keto
group with the OH on C5.
DMT 20053 – FOOD CHEMISTRY
 MONOSACCHARIDE
• Structural representations of sugars:
– Fisher projection: straight chain representations
– Haworth projection: simple ring in perspective
– Conformational representation: chair and boat
configurations

Fisher projection Haworth projection Conformational

representation
DMT 20053 – FOOD CHEMISTRY
 MONOSACCHARIDE
• Drawing a Haworth structure from a Fisher projection:
– Step 1: Draw a basic structure for the sugar

Fisher Haworth
– Step 2: Make sure if the sugar is D- or L- by looking the
carbonyl group at C5

DMT 20053 – FOOD CHEMISTRY

 MONOSACCHARIDE
– Step 3: If the sugar is a D-sugar, place a –CH2OH above the
ring on the carbon to the left of the oxygen, C5
* For an L-sugar, place it below the ring
CH2OH

CH2OH

D-sugar L-sugar

– Step 4: For an α-sugar, place an –OH below the ring on the

carbon to the right of the ring oxygen, C1
* For an β-sugar, place an –OH above the ring

DMT 20053 – FOOD CHEMISTRY

 MONOSACCHARIDE
CH2OH
CH2OH
OH

OH
α-D-sugar β-D-sugar

– Step 5: -OH groups on the right go below the ring and those
on the left, go above CH2OH

H H

H H
OH

OH OH

H OH

α-D-sugar

DMT 20053 – FOOD CHEMISTRY

 MONOSACCHARIDE
H OH H OH
4 6 H O H O
HO 5 HO
HO 2 H HO OH
3 H OH 1 H OH
H OH H H

-D-glucopyranose -D-glucopyranose

Because of the tetrahedral nature of carbon bonds,

pyranose sugars actually assume a "chair" or "boat"
configuration, depending on the sugar.
The representation above reflects the chair configuration
of the glucopyranose ring more accurately than the
Haworth projection.
DMT 20053 – FOOD CHEMISTRY
 DISACCHARIDES
• Two monosaccharide molecules linked
by a glycosidic (or acetal) bond:
– Maltose (glucose + glucose)
• Intermediate product of starch hydrolysis
• Found in starch from melting of barley
• Alpha 1-4 linkage fundamental for starch (link
between C1-C4 OH of 2 glucoses)

– Lactose (galactose + glucose)

• Milk sugar
• Found only in milk
• With (14) linkage from the anomeric OH of
galactose. Its full name is -D-
galactopyranosyl-(1 4)--D-glucopyranose

DMT 20053 – FOOD CHEMISTRY

 DISACCHARIDES
– Sucrose (glucose + fructose)
• Common table sugar
• Produced in leaves and stems of plants
• Found in sugar cane and sugar beets
• Because the configuration at the anomeric C of
glucose is  (O points down from ring), the
linkage is (12).
• The full name of sucrose is -D-glucopyranosyl-
(12)--D-fructofuranose.)

DMT 20053 – FOOD CHEMISTRY

 DISACCHARIDES
• Cellulobiose (glucose + glucose)
– Beta 1-4 linkage in cellulose
– Does not exist freely in nature

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 POLYSACCARIDES

• Heteropolysaccharide - composed of two or

more types of monosaccharides

• Homopolysaccharides - composed of one type

of monosaccharide
– Starch:
• Basic unit: alpha-D-glucose
• Principal sugar form in cereals

DMT 20053 – FOOD CHEMISTRY

 POLYSACCARIDES
• Starch granules
– Held together by H-bonds
– Insoluble in water
• Raw starch is not well digested
– Heat causes swelling of granules
• ‘Gelatinization’
• Access for digestive enzymes
• Retrograded starch - indigestible
crystalline form after cooling

DMT 20053 – FOOD CHEMISTRY

 POLYSACCARIDES
• Starch structure:
– Natural starch
conformation
• Mixture of
amylose and
amylopectin
• Pure amylose not
natural (only
85%)
• Waxy maize
starch –
amylopectin

DMT 20053 – FOOD CHEMISTRY

 POLYSACCHARIDES
• Two forms of starch:
1. Amylose
• Apha 1-4 linkages
• Straight chain
• 14-30% of total plant starch
• Water soluble

DMT 20053 – FOOD CHEMISTRY

 POLYSACCHARIDES
CH2OH CH2OH
H O H H O H amylopectin
H H
OH H OH H 1
O
OH
O
H OH H OH

CH2OH CH2OH 6 CH2 CH2OH CH2OH

H O H H O H H 5 O H H O H H O H
H H H H H
OH H OH H OH H 1 4 OH H OH H
4 O O
O O OH
OH 2
3
H OH H OH H OH H OH H OH

2. Amylopectin
– Alpha 1-4 linkages with alpha 1-6 linkage at branch points
– 70-85% total plant starch
– Not water soluble

DMT 20053 – FOOD CHEMISTRY

 POLYSACCHARIDES
• Starch composition:
TYPE OF AMYLOSE % AMYLOPECTIN
STARCH %
MAIZE 26 74
WHEAT 25 75
RICE 17 83
POTATO 21 79
CASSAVA 17 83
WAXY MAIZE 1 90
HIGH AMYLOSE 70 30

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 POLYSACCHARIDES
• Starch configuration:
– 3D structure
– Not soluble in cold
water
– Settles
– No adhesive power
– No binding capacity

DMT 2023 – FOOD CHEMISTRY

 POLYSACCHARIDES
• Changes of starch during processing:
– Gelatinization: disruption of molecular order within
granules. When heated in water,they can swell slightly, and
then return to their original size on drying.
– Gel forming: gel is a continous , 3-dimensional network of
connected molecules or particles. Gels have some
characteristics of solids and liquids. The 3-D network offers
significant resistance to an applied stress causing it to
behave as an elastic solid.
– Retrogradation : cooling a hot starch paste produces a
viscoelectric, firm and rigid gel. As starch pastes are cooled
and stored, the starch becomes progressively less soluble.

DMT 2023 – FOOD CHEMISTRY

 POLYSACCHARIDES
– Syneresis: refers to expulsion of liquid from the gel. In a
polymer, lowering of solvent quality ( e.g by changing
temperature ), adding salt, or increase in number of cross-
links or junction may cause synerisis.

DMT 2023 – FOOD CHEMISTRY

 POLYSACCHARIDES
• Starch gelatinization:
– Gelatinization only occurs with heat and water
– Heating causes the following:
– Water absorption by amyloplasts
– Rupturing of the amyloplast
– Starch network formed
– Hydrated network with water pockets
– Point at which rupture occurs differs
– Gelatinization!

DMT 2023 – FOOD CHEMISTRY

 POLYSACCHARIDES
• 5% Corn starch = start of • At 40oC more water as
heating only has water absorbed and granules
absorbed onto granule start to separate
surfaces
• Granules still clumping

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 POLYSACCHARIDES
• At 65oC more water • At 70oC further rupture,
as absorbed and leakage
granules start to
rupture

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POLYSACCHARIDES

DMT 2023 – FOOD CHEMISTRY

 POLYSACCHARIDES
• Factors affecting gelatinization:
– Water content
– Starch concentration
– Nature of starch
– Degrading enzymes
– Fat
– Protein
– Temperature
– Hydrogen bonds

DMT 2023 – FOOD CHEMISTRY

 POLYSACCHARIDES
• Glycogen
– the glucose storage polymer in animals, is similar in structure to
amylopectin.
– But glycogen has more a(16) branches.
– The highly branched structure permits rapid glucose release from glycogen
stores, e.g., in muscle during exercise.
– The ability to rapidly mobilize glucose is more essential to animals than to
plants.
C H2OH C H2OH
H O O
glycogen
H H H
H H
OH H OH H 1
O
OH
O
H OH H OH

C H2OH C H2OH 6 C H2 C H2OH C H2OH

H O H H O H H 5 O H H O H H O H
H H H H H
OH H OH H OH H 1 4 OH H OH H
4 O O
O O OH
OH
3 2
H OH H OH H OH H OH H OH

DMT 2023 – FOOD CHEMISTRY

 POLYSACCHARIDES
CH2OH 6CH OH CH2OH CH2OH CH2OH
2
O 5 O O H O H O OH
H H H
H H H H H
OH H 1 O 4 OH H 1 O OH H O OH H O OH H
OH H H H
H 2 H
3
H OH H OH H OH H OH H OH
cellulose

•Cellulose:
•A major constituent of plant cell walls, consists of long linear
chains of glucose with (14) linkages.
•Every other glucose is flipped over, due to  linkages.
•This promotes intra-chain and inter-chain H-bonds and van
der Waals interactions, that cause cellulose chains to be
straight & rigid, and pack with a crystalline arrangement in
thick bundles - microfibrils.

DMT 2023 – FOOD CHEMISTRY

 DETERMINATION
• Carbohydrate determination:
– Chemical reaction
• Lane-Eynon method
• Munson & Walker method
• Alkaline Ferycynide method
• Sulfuric acid-phenol method
• Anthrone method
– Enzymatic reaction
– Physical method
• Polarimetry
• Reflective Index
• Specific gravity

DMT 2023 – FOOD CHEMISTRY

 DETERMINATION
• Carbohydrate determination:
– Modern method
• High Performance Liquid Chromatography (HPLC)
• Gas Cromatography (GC)
• Mass Chromatography
• Nuclear Magnetic Resonance Spectometry
• Immunoassay
• Supercritical Fluid Cromatography

DMT 2023 – FOOD CHEMISTRY

 DETERMINATION
• Polarimetry:
– Measurement of optical activity in chiral or asymmetric molecules
using plane polarized light.
– Molecules may be chiral because of certain atoms or because of chiral
axes or chiral planes
– Measurement uses an instrument called a polarimeter (Lippich type)
– Rotation is either (+) dextrorotatory or (-) levorotatory

DMT 2023 – FOOD CHEMISTRY

DETERMINATION

DMT 2023 – FOOD CHEMISTRY

 DETERMINATION
• Magnitude of rotation depends upon:
– the nature of the compound
– the length of the tube (cell or sample container) usually
expressed in decimeters (dm)
– the wavelength of the light source employed; usually either
sodium D line at 589.3 nm or mercury vapor lamp at 546.1
nm
– temperature of sample
– concentration of analyte in grams per 100 ml

DMT 2023 – FOOD CHEMISTRY

 DETERMINATION
 observed x 100
[] D
T
=
l xc
• D = Na D line
• T = temperature oC
•  obs : observed rotation in degree (specify solvent)
• l = length of tube in decimeter
• c = concentration in grams/100ml
• [] = specific rotation

DMT 2023 – FOOD CHEMISTRY