FST3107-INTRODUCTION TO

FOOD CHEMISTRY

CARBOHYDRATES
 TOPIC OBJECTIVES

Student will be able to explain the chemical and

physical properties of carbohydrate and relationship
of its structure with functions in food.
 Producer of Carbohydrate

Carbohydrate
(glucose)
 DEFINITION AND SOURCES

Carbohydrates (also called saccharides) is a

Greek word for 'sugar‘.

It consists of polyhydroxy aldehydes or

ketones. These compounds involve in
hydrolysis of sugar.

Three elements; carbon, hydrogen and oxygen.

Widely distribute in plant.

 WHY DO WE NEED CHO?

a. A source of energy for the body e.g. glucose

and a store of energy, ATP, starch in plants

b. Building blocks for polysaccharides (giant

carbohydrates), e.g. cellulose in plants and
glycogen in the human body

c. Components of other molecules e.g . DNA,

RNA, glycolipids, glycoprotein.
STRUCTURE OF CHO
Monomer of Carbohydrate
 Monosaccharides = Monomer of carbohydrate

• Classified by:
– A. Aldose or ketose
– B. Number of carbons in chain
– C. Configuration of chiral carbon farthest from the carbonyl
group

Aldose (a) Ketose (b)

 B. Number of carbons in chain

Functional group
Number of carbon Aldehyde Ketone

3 Triose Trulose
4 Tetrose Tetrulose
5 Pentose Pentulose
Number of carbons

6 Hexose Hexulose
7 Heptose Heptulose
8 Octose Octulose

Trioses (C3H6O3) Glycerose Dihydroxyacetone

  (glyceraldehyde)
Tetroses (C4H8O4)  Erythrose Erythrulose
Pentoses (C5H10O5)  Ribose Ribulose
Hexoses (C6H12O6)  Glucose Fructose
A. Aldose or ketose group
 C. Configuration of chiral carbon farthest from the carbonyl
group
• A carbon is chiral if it has four different groups
• Chiral compounds have the same composition but are not superimposable
• Display in Fisher projection

CHO CHO
H OH HO H
CH2OH CH2OH

D-glyceraldehyde L-glyceraldehyde

Note: The Fischer projection, devised by Hermann Emil Fischer in 1891, is a two-
dimensional representation of a three-dimensional organic molecule by
projection
Enantiomer is a molecular that will not have two-mirror image
forms.
Linear and Cyclic of Carbohydrate (configuration)
 1
CH2OH

2C O

HO C H
1 CH2OH
3 HOH2C 6 O
H C OH
4 5 H HO 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.
 6 CH2OH 6 CH2OH
5 O 5 O
H H H OH
H H
4 H 1 4 H 1
OH OH
OH OH OH H
3 2 3 2
H OH H OH
-D-glucose -D-glucose

Cyclization of glucose produces a new asymmetric center at C1.

The 2 stereoisomers are called anomers, a & b.

Haworth projections represent the cyclic sugars as having

essentially planar rings, with the OH at the anomeric C1:
 a (OH below the ring)
 b (OH above the ring).
Take 5
 CLASSIFICATION OF CHO

Monosaccharides (e.g. glucose)

Disaccharides (e.g. sucrose) are relatively

small molecules.

Polysaccharides; other carbohydrate

molecules, very large in size (e.g. starch and
cellulose).

They are often called sugars.

 Monomer of Carbohydrate

Monomer is smallest molecular unit :

glucose, fructose, galactose
 Monomer of “nasi lemak” (?)

‘Sambal’- spicy
sauce

rice cooked
in
coconut cucumber
milk
boiled/fried egg

side dish
-chicken/squid/shrimp/cockle
 SIMPLE CARBOHYDRATES

• Simple carbohydrates have a 'simple' molecular structure and are

made up of 1-2 sugar molecules. The simplest form of carbohydrate is
glucose.

• Simple sugars that are found in foods include sucrose (table sugar),
fructose (found in fruit), and lactose (found in milk).

• Sugar, honey, fruit, fruit juice

 MONOSACCHARIDES

Monosaccharides are the simplest carbohydrates and are often called

single sugars.

They are the building blocks from which all bigger carbohydrates are
made.

Monosaccharides have the general molecular formula (CH2O)n, where n

can be 3, 5 or 6.

Monosaccharides (from Greek monos: single, sacchar: sugar) are the

most basic units of biologically important carbohydrates.

They are the simplest form of sugar and are usually colorless, water-
soluble, crystalline solids.

Some monosaccharides have a sweet taste.

Examples of monosaccharides include glucose (dextrose), fructose,

galactose, xylose and ribose
MONOSACCHARIDES
Most stable conformation
 Disaccharide
Monosaccharide + monosaccharide = disaccharide

Glycosidic Bonds
A glycosidic bond is a type of covalent bond that joins a carbohydrate
(sugar) molecule to another group, which may or may not be another
carbohydrate.

Formation of ethyl glucoside : Glucose and ethanol combine to form

ethyl glucoside and water. The reaction often favors formation of the
α glycosidic bond as shown due to the anomeric effect
A disaccharide or biose is the carbohydrate formed when two
monosaccharides undergo a condensation reaction which involves the
elimination of a small molecule, such as water, from the functional
groups only.
Disaccharide
Caramel
Properties of Mono- and Disaccharides
The Relative of Sweetness of Sugar
(Sucrose = 1.00)
 Oligosaccharide

An oligosaccharide (from the Greek oligos, a few, and sacchar, sugar) is a

saccharide polymer containing a small number (typically three to ten) of
component sugars, also known as simple sugars (monosaccharides).
 Raffinose
Raffinose is a trisaccharide composed of galactose, fructose, and
glucose. It can be found in beans, cabbage, brussels sprouts, broccoli,
asparagus, other vegetables, and whole grains. Raffinose can be
hydrolyzed to D-galactose and sucrose by the enzyme α-galactosidase
(α-GAL), an enzyme not found in the human digestive tract. α-GAL also
hydrolyzes other α-galactosides such as stachyose, verbascose, and
galactinol, if present. The enzyme does not cleave β-linked galactose, as
in lactose.
Others Oligosaccharide
Complex Carbohydrates

(e.g. rice, wholemeal,pasta)

Complex carbohydrates are also made up of sugars, but the sugar molecules
are form longer, more complex chains. Complex starchy carbohydrates
include whole grains, peas and beans, which are rich in vitamins, minerals an
fiber.
• Plants store glucose as amylose or amylopectin, glucose
polymers collectively called starch.
• Glucose storage in polymeric form minimizes osmotic effects.
• Amylose is a glucose polymer with a(14) linkages.
• The end of the polysaccharide with an anomeric C1 not
involved in a glycosidic bond is called the reducing end.
Complex Fibrous Carbohydrates (Fiber)

(e.g. most vegetables)

Fibrous carbs are rich sources of vitamins, minerals, phytochemicals and

other nutrients and tend to be green vegetables. These are full of fiber,
which is the indigestible portion of plant material (i.e. vegetables).
Products Sugar Source

D-Glucose Fruit juices, hydrolysis of

starch, cane or beet sugar,
maltose and lactose

D-Fructose  Fruit juices, honey,

hydrolysis of cane or beet
sugar and inulin, enzymic
isomerization
of glucosesyrups for food
manufacture

D-Galactose  Hydrolysis of lactose

D-Mannose  Hydrolysis of plant mannan
gums
NATURAL POLYSACCHARIDE
 NATURAL POLYSACCHARIDE

Found in small packets called granules.

 Oat  Bean  Potato  Maize  Rye  Barley

 Glycemic Index (GI)

The glycemic index, glycaemic index, or GI is a measure of the effects

of carbohydrates on blood sugar levels. Carbohydrates that break
down quickly during digestion and release glucose rapidly into the
bloodstream have a high GI; carbohydrates that break down more
slowly, releasing glucose more gradually into the bloodstream, have a
low GI.
FIBER
 DIETARY FIBER

 Important food component

 Complex mixture

 Resistant to hydrolysis by endogenous enzymes

 1, -4 glycosidic linkages

sum of polysaccharides and lignin that is not

digested by endogenous secretions of human
digestive tracts
 TYPES OF DIETARY FIBER

CELLULOSE
 A linear polymer of glucose with beta –1-4 links(main
structural component of plant cell walls).
 Insoluble in water.
 Bulking and rheological agent in low-calorie foods.
 Chemical modifications of cellulose-based food gums.

BETA-GLUCANS
 Gulcose polymers containing both beta, 1-3 links and beta 1-4
links in various proportions depending on source.
 Less linear, more soluble than cellulose.
 Contribute to viscosity of products.
 TYPES OF DIETARY FIBER

LIGNIN
 Highly complex nonpolysaccharide
 Phenylpropane units derived from various phenolics
 Insoluble

PECTINS
 polymer galacturonic acid (200-1000 unit) bounded by alpha, 1-
4 galacturonic links.
 Special property is ability to produce strong gels.
 TYPES OF DIETARY FIBER

HEMICELLULOSE

 Heterogenous group of polysaccharides.

 Contain variety of different sugars in the backbone chain and
side chain.
 Includes arabinoxylans, galactomannans and xylogiucans.
 Soluble in dilute alkali.
 Improve water binding in baked goods.
 TYPES OF DIETARY FIBER

CHITIN/CHITOSAN
 Cellulose-like constituents, inserts
 Poly beta, 1-4 acetyl-D-glucosamine
 Deacetylation of chitin will form chitosan

PLANT GUMS
 Water-soluble polysaccharides
 Contribute to viscosity or gelling properties
 Guar, locust gum (seeds), plant exudates of gum arabic and
seaweed-derivedgums like agar and carrageenan and algin.
 Widely used as thickening agents.
 FUNCTIONAL PROPERTIES OF
DIETARY FIBER

Dietary Fiber Example

Viscosity Guar, locust bean, carrageenan,
Xanthan
Bulking Guar, locust bean gum
Agent/Thickener
Emulsifier Aracbic, xanthan, guar
Gel Formation Pectin, Carrageenan, Alginate
Flavour Carrier Gum Arabic, Cellulose
Humectant Carrageenan
 Take5…
Next is reactions related to CHO
1.Condensation Reaction/ Glycoside Formation

D-glucopyranosyl + D- fructofuranoside ---> sucrose

 2.Oxidation Reaction

 Like all other aldehydes, aldose sugars are easily oxidized to yield

carboxylic acids.
 Tollens' reagent (Ag+ in aqueous ammonia), Fehling's reagent (Cu

in aqueous sodium tartrate) and Benedict's reagent (Cu in

aqueous sodium citrate).
 test for reducing sugars.

 ketoses that are reducing sugars as well.

 fructose reduces the Tollen's reagent because fructose is readily

isomerized to an aldose in basic solution by a series of keto-enol

tautomeric shifts.
 Reduction of Monosaccarides

 Carbonyl group is reduced to an alcohol by a metal

catalyzed reaction of hydrogen gas under pressure.
 3.INTERACTION WITH WATER

 Uncooked, undamaged starch grains if put in cold water--- >water uptake

and swelling limited.

 Heating starch in excess water --- > Granules swell enormously

 Phenomenon called “Gelatinization” Kinetic energy of water great

enough to overcome the attraction between the starch molecules.

 Gelatinization Temp. varies with source (complete at>95C, 203F)

 Opaque --- > Translucent

 Lose birefringence and initiate thickening of liquids

 Amylose (dispersible in hot H 20) escape from swollen granules.

 Dried and have ability to reabsorb large amounts of water

 Instant rice, Mashed Potatoes

 4.RETROGRADATION OF AMYLOSE

 Leached Amylose molecules stay dispersed in liquid paste as

long as it remains hot.

 When temp, drops, kinetic energy no longer great to

counteracts the tendency of amylose molecules to

reassociate.
 Amylose molecules rebond to one another and to other

starch components on outer edges of the granules.

 Thus, the swollen starch grains unites in a network

 This recrystallization of gelatinized starch is known as

“Retrogradation”
Gelatinization Retrogradation

starch grains
 5.SYNERESIS

 Part of the water firmly bonded to starch molecules on the

surface of swollen grains and some to the amylose molecules

 The bulk of the water is free, trapped by the network of the of

swollen starch grains

 Some of the water will seep from the interstices.

 This leakage of water from a gel is termed “syneresis”

 5. HYDROLYSIS

 Important in food processing/preservation techniques

 High-Fructose-Corn Syrup (HFCS)

 Beverages/confections

 Degree of conversion to D-glucose measured as dextrose equivalent (DE)

 Dextrose Equivalence is a quantitative measure of the degree of starch

polymer hydrolysis. It is a measure of reducing power compared to a

dextrose standard of 100.
 The degree of hydrolysis affects the functional properties of maltodextrins

(MD) and corn syrup solids (CSS). The higher the DE, the greater the
extend of hydrolysis and the greater changes in functional properties.
5. FACTORS AFFECTING HYDROLYSIS

 Hydrolysis is the cleavage of glycoside linkages in acidic or

alkaline media.

 The rate determining step of this reaction is the loss of ROH

and the formation of the resonance stabilized carbonium ion.

 Since carbohydrates unstable in foods especially if subject to

high temperatures or high acidity.

 the rate of hydrolysis is proportional to the degree of

association between polysaccharide molecules.

 rate limiting
step

Carbonium ion
 6. BROWNING REACTIONS

Enzymatic

 By enzyme polyphenols oxidase

 In the present of three components (oxygen + Phenolic + PPO)

Nonenzymatic

 Chemical reactions

 In the present of heat

 Caramelization

 Maillard reaction
 CARAMELISATION

 Heat induced transformation of reducing sugars alone in a

concentrated solution

 lose water molecules from their structure through a process

called "1:2 & 2:3-enolisation".

 Influenced by pH

 Through many intermediates, and in the pH 2-7 range, D-fructose

for example can give rise to the Furans, Isomaltol and Maltol

 Well known bread crust flavour/aromas.

STEP IN CARAMELISATION PROCESS

 Direct heating of carbohydrate esp. sugar/syrup ---------

complex

 Anomeric shifts, alteration of ring size, breakage of glycosidic

bonds

 Dehydration followed by formation of anhydro rings, double

band formation(furans)

 Unsaturation induce condensation and polymerize ring

system (color and flavour)
STEP IN CARAMELISATION PROCESS

 Direct heating of carbohydrate esp. sugar/syrup ---------

complex

 Anomeric shifts, alteration of ring size, breakage of glycosidic

bonds

 Dehydration followed by formation of anhydro rings, double

band formation(furans)

 Unsaturation induce condensation and polymerize ring

system (color and flavour)
 CHANGES DURING CARAMELISATION PROCESS

 Caramelization occurs during dry heating and roasting of

foods with a high concentration of sugars.
 Removal of water, isomerization and polymerisation steps
complex series of chemical reactions.
 Melting of the sugar at high temperatures, followed by
foaming (boiling).
 Saccharose decomposes into glucose and fructose.
 The next step is the isomerization of aldoses to ketoses and
further dehydration reactions.
 The last series of reactions include both fragmentation
reactions (flavour production) and polymerization reactions
(colour production)
 Caramelization starts at relatively high temperatures as
compared to the other browning reactions, and depends on
the type of sugar
 TEMPERATURE FOR CARAMELISATION PROCESS

 Fructose= 110° C

 Galactose = 160° C
 Glucose=160° C

 Maltose =180° C

 Saccharose=160° C
 Maillard Browning
• “the sequence of events that begins with
reaction of the amino group of amino acids
with a glycosidic hydroxyl group of sugars;
the sequence terminates with the
formation of brown nitrogenous polymers
or melanoidins”
– John deMan
 MAILLARD REACTION

 Amino-containing Compound (protein) +sugar+H2O ---

colorless solution (initial) ---- yellowish (intermediate) ----

red-brown to dark brown (strong aroma) called melanoidins.

Important in controlling Maillard

1. Loss of amino acid (Lysine)

2. Undesirable dark color and strong flavour and odour

3. Possible toxicity of products (nitrosamine:mutagenic)
 Desirable Consequences

 Characteristic flavors
eg cereal beer, coffee, some candies, chocolate, tea

 Brown colors
toasting of cereals, roasting of meats,
vegetables (eg potato), chocolate, some candies, coffee, beer

 Increased palatability/nutrition - indicator of doneness

 Generation of antioxidants/anticarcinogens
 Undesirable Consequences

 Darkening of the foods

 Loss of solubility of proteins

 Loss of protein biological value (destruction of eaa)

 Toxicity/mutagenicity generated
Addition of an amine to an aldose
(glycosylamine)
The Amadori Rearrangement
 DH – A Crucial Intermediate

Amines

Strecker aldehydes Polymerize

Pyrolytic products
 Strecker Degradation

O O O
R -H2O -H2O O
COOH R
O H2N N -H2O H
OH
H
H R Stecker aldehyde
dicarbonyl amine NH3 CO2
COOH

O O O
R -H2O -H2O O
COOH R
O H2N N -H2O H
OH
H
H R Stecker aldehyde
dicarbonyl amine NH3 CO2
COOH
Rich nutty, meaty flavors
Mutagens from the Maillard Reaction

Asparagine

O CH2
C O
H
H2N CH
O
Strecker aldehyde C
H2N H2

Acrylamide
 Control Steps

• Rapidly accelerated by temperature

• Significant acceleration at intermediate water
activities
• Sugar type
– Pentose>hexose>disaccharide>>polysaccharide
• protein concentration (free amines)
• Inhibited by acid
– amines are protonated
– and used up, pH drops
• Sulfur dioxide
• Metals like Cu and Fe enhance browning (later
steps may involve oxidation-reduction reaction)
 FACTORS AFFECTING REACTION

1. pH—insignificant in strongly acidic solutions.

(prononated amino group prevent formation of
glycosylamine)
2. Maximum reaction rate occur at intermediate water
activity.
3. Metals like Cu and Fe enchance browning (later
steps may involve oxidation-reduction reaction)
4. Temperature—lower temp. reduce browning
5. Removing one of substrates of reaction—usually
sugar.) (glucose oxidase)
6. Sulfur dioxide or sulfites inhibit browning
 PYROLYSIS

scorching, (from the greek "pyro" - burning) and

involves the total loss of water from the sugar
molecule and the breaking of carbon-carbon linkages
the *destruction* of the sugar molecule
result is a burnt and inedible flavor.
 DEHYDRATION AND THERMAL
DEGRADATION

 Important in foods
 Anomerization
a or b –D-gucose  a or b equi.
 Aldose-ketose interconversion
D-gucose  D-fructose
 Bond cleavage
Pentoses 2-furfural
Hexoses 5-hydroxymethyl-2-fural
Other products 2-hydroxyacethylfuran Isomaltol
Further fragmentation will produce: levulinic acid,
formic acid, diacetyl, lactic acid, pyruvic
Highly odorous and desirable/undesirable flavour
Induced by high temp. (processed fruit juice)
Toxicities of these products studied
(Furfural>HMF)
End