LESSON 2

PART 1:
STRUCTURE AND TECHNICAL PROPERTIES
OF NATIVE STARCH

Lecturer: Nguyễn Đặng Mỹ Duyên

2/2022
 DEFINITION OF STARCH

 Roots/Tubers
 Potato
 Arrowroot
 Tapioca
 Cereal
 Corn
 Waxy corn
 Wheat
 Rice
 Waxy rice
Starch Granule

Potato starch Rice starch Kidney bean starch

(Bar: 50 µm) (Bar: 2 µm) (Bar: 20 µm)

Amaranth starch Arrowroot starch Buckwheat starch

(Bar: 1 µm) (Bar: 20 µm) (Bar: 5 µm)

Cassava starch Corn starch Oat starch

Granule Structure
Granule Structure
Starch Composition

 Starches usually contain more

amylopectin than amylose
 Generally roots/tubers contain more
amylopectin than cereals
 Roots/Tubers: 80% amylopectin
 Cereals: 75% amylopectin
Starch Composition

Starch % amylose % amylopectin

Tapioca 17% 83%
Potato ~20% ~80%
Wheat 25-26% ~75%
Corn 24-28% ~75
Waxy corn ~0% ~100%
Hi amylose ~ 75% ~ 25%
Rice 22% 78%
Amylose

 Linear component
of starch
 Contains 1,4-
alpha-glucosidic
bonds
 Molecular weight:
less than 0.5
million
 Can form coils
which will trap
iodine and turn
blue
Amylose
Amylopectin
 Branched
component of starch
 Contains 1,4-alpha-
glucosidic as well as
1,6-alpha-glucosidic
bonds
 Molecular weight:
50-500 million
 Limited coiling
causes purplish-red
color when iodine
added
FUNCTION PROPERTIES OF STARCH

 Gelatinization (hồ hóa)

 Dextrinization (dịch hóa)
 Gelation (tạo gel)
Gelatinization
 When starch is heated in water
 Hydrogen bonds break, allowing water to enter the
granule pthe granule swells
 Amylose migrates out of the granule
 H-bonding between water and amylopectin increases
 Reduced free water changes the viscosity of the
starch mixture, thickening it
 • Tinh boät baép 5% 300C • Tinh boät baép 5% 500C
• NGUYEÂN LIEÄU
• Tinh boät baép 5%
400C

• • • • Tinh boät baép 5% 750C

Tinh boät baép 5% 600C Tinh boät baép 5% 650C Tinh boät baép 5% 700C

• Tinh boät baép 5% 900C

• Tinh boät baép 5% 800C • Tinh boät baép 5% 850C
Gelatinization and Temperature
 Gradually thicken with temperature
 Can be heated to 100oC without much granule
rupture
 If held at 95oC will implode and lose viscosity
Gelatinization
 Best thickening ability:
potato starch
 Worst thickening ability:
wheat starch
 More amylopectin=more
translucent (độ truyền suốt)
=more stringy (độ dai)
Viscosity and Type of Starch
Gelatinization and Sugar
 Sugar competes with the starch for water so less water
available for gelatinization
 Delays gelatinization and decreases viscosity
 Increases gelatinization temperature
 The more sugar added, the longer the delay
 Disaccharides have a stronger effect than monosaccharides
 Gelatinization and Acid
 Used together in fruit pie fillings, specifically lemon fillings
 Acid breaks down starch molecules so the paste is thinner
 Decreases viscosity
 Acid effect can be minimized by adding after gelatinization or heating
rapidly
 Gelation
 As a starch paste cools, a gel is formed
 Free amylose molecules lose energy as the temperature decreases and
form hydrogen bonds
 The bonds create a network that holds the swelled granules in place
Gelation
 Gelation and Starch Source
 The more amylopectin (less amylose),
the softer the gel
 Potato starch = high amylopectin=good
thickening agent=soft gel
 Dent corn starch=less
amylopectin=less effective thickening
agent=strong gel

Tapioca starch gel

 Gelation and Other Effects
 Heating
 Moderate temperature and rate of heating
 Enough amylose needs to be released from the
granule without the granule bursting

 Agitation (sự hỗn loạn)

 Agitation during cooling disrupts amylose network
 Should mix flavorings immediately after removing from
heat
Gelation and Other Effects

 Sugar
 Decreases gelatinization and amylose
release
 harder gel

 Acid
 Decreases gelatinization by hydrolysis of
granules
 Softer gel
 Aging Gels
 Syneresis (mức độ tách nước)
 Loss of water from a gel
 Amylose molecules pull together, squeezing water out

 Retrogradation (sự thoái hóa)

 Realignment of amylose molecules
 Hydrogen bonds break and reform into more orderly
crystals
 Can by reversed by gently heating
 Examples: refrigerated pudding, stale bread
Uglification
 WATER

This picture ignores swollen and collapsed

granules.
Junction zones will naturally enlarge over time or
in response to processes such as freezing.
 WATER

+ WATER of SYNERESIS that has been

squeezed out of the gel structure

The texture gets very ugly when this happens.

Retrogradation (sự thoái hóa)
Dextrinization
 When starch is heated without water
 A higher temperature is reached than with water
 Bonds break throughout the starch forming dextrins
Starch hydrolyzation
Sự thủy phân tinh bột
 -amylase

• breaks -D-(1→4) linkages, endo-acting enzyme (attacking

the starch chain in the interior part)
• the resulted product: mixture of oligosaccharides
+ maltose + glucose; on the branching:
isomaltose and panose  viscosity fall; content of
reducing matters increases slowly
 -amylase

• breaks -D-(1→4) linkages as well, exo-acting enzyme – it

acts on the non-reducing ends of starch polymer chains and
produces maltose, it stops on the branching -D-(1→6) –
formation of limit dextrins
• viscosity falls slowly, DE increases very fast
 glucoamylase

• breaks -D-(1→4) and -D-(1→6) linkages, the linkage -

D-(1→6) is split more slowly
• exo-acting enzyme  it acts on the non- reducing ends of
starch polymer chains and produces glucose
• DE increases
 Pollulanase isomaltase

• break -D-(1→6) linkages in amylopectin,

• linear chains of amylose remain in solution
after hydrolysis
PART 2: MODIFIED STARCH
 Definition of modified starch
 Modified starch, also called starch derivatives, are
prepared by physically, enzymatically, or chemically
treating native starch, thereby changing the
properties of the starch.
 Why native starch should be modified?
 Processing at high temperature
 Mechanical Shear
 Acid Media
 Salts
 Low Temperature
 Starch Modification
 Improving the cooking properties
 Decreasing the retrogradation tendency
 Improving the freeze-thaw stability of paste
 Decreasing the paste and/or gel syneresis
properties
 Increasing the paste and/or gel clarity
 Increasing the paste and/or gel textures
 Improving the film forming
 Improving the adhesion properties
 Improving the hydrophobic group (for emulsion
stabilization)
Types of modified starch

 E1401 Acid-treated starch

 E1402 Alkaline-treated starch
 E1403 Bleached starch
 E1404 Oxidized starch
 E1405 Starches, enzyme-treated
 E1410 Monostarch phosphate
 E1411 Distarch glycerol
 E1412 Distarch phosphate esterified with sodium
trimetaphosphate
 Starch Modification

 E1413 Phosphated distarch phosphate

 E1414 Acetylated distarch phosphate
 E1420 Starch acetate esterified with acetic anhydride
 E1421 Starch acetate esterified with vinyl acetate
 E1422 Acetylated distarch adipate
 E1423 Acetylated distarch glycerol
 E1440 Hydroxypropyl starch
 E1442 Hydroxypropyl distarch phosphate
 Starch Modification

1. Ch e m i c a l m odi f i c at i on
Cross linking
Esterification Acid
t r e a t m e n t Oxidation
2. P h y s i c a l m odi f i c at i on
Heat- moisture t r e a t m e n t
Retrogradation
Pregelatinization
3. E n z y m a t i c m odi f i c at i on
1.Chemical modification
Etherification of native starch
 E1440 Hydroxypropyl starch
 Etherification of native starch
 The food grade hydroxypropylated starches are generally prepared
by etherification of native starch with propylene oxide in the
presence of an alkaline catalyst.

 The hydroxypropyl groups introduced into the starch chains are

capable of disrupting the interand intra-molecular hydrogen bonds
thereby weakening the granular structure of starch, leading to an
increase in motional freedom of starch chains in amorphous regions
Etherification

Hydroxypropyl starch (E1440)

 Etherification
 Improved clarity of starch paste, greater
viscosity, reduced syneresis and freeze-thaw
stability
 Used as thickeners in fruit pie fillings, puddings,
gravies, sauces, and salad dressings...
 Esterification
 Starch ester is a kind of modified starches in which some
hydroxyl groups have been replaced by ester groups.

 Esterification can impart hydrophobicity to starch products

by the substitution of free available hydroxyl groups
Esterification
 Starch acetate (E1420, E1421):
Esterification with acetic anhydride or vinyl
acetate.
 Acetylated distarch adipate (E1422)
Esterification with acetic anhydride and
adipic anhydride.
 Starch sodium octenylsuccinate (1450):
Esterification by octenylsuccinic anhydride.
Esterification
Esterification
Properties:
 Lower gelatinization temperature and
retrogradation
 Lower tendency to form gels and higher paste
clarity.
 Increasing the degree of swelling or hydration
capacity, & by reducing retrogradation
 Esterification
 Benefit to user :
 Excellent chill and freeze-
thaw stability to extend shelf
life.
 Easy to cook in high solid
system
 Application :
 Refrigerated & frozen foods
 High brix fillings & toppings
 Cross-linking Starch
 Chemical modification of starch that
results in covalently bonded inter- and
intramolecular bridges between starch
polymers.

 Cross-linking is generally performed by

treatment of granular starch with
multifunctional reagents capable of
forming either ether or ester inter-
molecular linkages between hydroxyl
groups on starch molecules
 Cross-linking Starch
• Cross – linking agents: Sodium trimetaphosphate
(STMP), monosodium phosphate (SOP), sodium
tripolyphosphate (STPP), epichlorohydrin (EPI),
phosphoryl chloride (POCL3), a mixture of adipic
acid and acetic anhydride, and vinyl chloride

 E1410 Monostarch phosphate

 E1412 Distarch phosphate
 E1413 Phosphated distarch phosphate
 ………………..
Cross-linking Starch

Distarch phosphate
Cross-Linking Starch

Phosphated distarch phosphate

Cross-Linking Starch

E1414 Acetylated distarch phosphate

Cross-Linking Starch

E1442 Hydroxypropyl distarch phosphate

Cross-Linking Starch

Properties
 Resists viscosity breakdown
 Resists prolonged heating effects
 Resists high shear rates
 Resists high acid environments
 Increased viscosity
 Increased texture
 To bind ingredients together & acting as a thickener for
soups.
 Helping powdered foods, like powdered cheese sauce &
gravy, have a less lumpy consistency when mixed.
 Serving as a fat substitute for low-fat foods.
 Acting as an emulsifier & stabilizer for salad dressings in
order to keep oils from separating.

 Oxidation
 The major reactions of oxidation of starch include cleavage
of polymer chains and oxidation of hydroxyl groups to
carbonyl and carboxyl groups

 Introduce carbonyl group and carboxyl groups which

increases clarity and reduces retrogradation of cooked
starch pastes
 Provide lower viscosity & low temperature stability
Oxidation
Properties
 increases clarity and reduces retrogradation
of cooked starch pastes
 Provide lower viscosity & low temperature
stability
Oxidation
Benefit to user
 Improves adhesion of coatings
 Creates soft stable gels at higher dosage
than parent native starch.
Application : Battered meat, poultry & fish
(crispy texture after frying); confectionary
Major
Physical modification

 Pregelatinization
 Heat- moisture treatment
 Irradiation and microwave
 High pressure processing
 Pregelatinized Starch

 Starch has been previously gelatinized

and dried to powder form.
 fully pregelatinized
 partially pregelatinized.
Pregelatinized Starch
Pregelatinized Starch
METHOD
 Drum drying (starch suspension or starch gels)
 €Extrusion (semi-dry starch)
 Spray drying (starch suspension)
 Pregelatinized Starch
Benefit to user:
Cold-water thickening eliminates need to cook,
offers convenience and energy saving.
Application:
 Instant soups, sauces, dressing, desserts,
bakery mixes.
 Thickener in food that receive minimal heat
processing.
 Thermal treatment Starch
 Physical modification of starch without any gelatinization,
damage to granular integrity or loss of birefringence.
 Thermal treatment involved starch extraction in excess
water and lower temperatures than starch gelatinization
temperatures.
 Starch is also heated above gelatinization temperature
but with insufficient moisture for gelatinisation
 Thermal treatment Starch
Objectives:
 Strengthen starch granule
 Delay viscosity development by retarding
granule swelling
Thermal treatment Starch
Thermal treatment Starch
Benefit to user:
 Unique functional native starch
 Improved process tolerance to heat, acid,
and shear
Application: Ambient stable products; bottled
sauces; sterilized soups and sauces.
Enzymatic modification of starch

 Currently, only hydrolases (amylases)

are used to modify starch. The use of
amylases to produce products derived
from hydrolysis of starch is described in
Fig 3.3
Enzymatic modification

Fig 3.3:
Enzymatic modification of starch
Enzymatic modification of starch