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Starch as a Hydrocolloid Why is starch is the most important food thickener? John Mitchell John.Mitchell@biopolymersolutions.co.,uk

Starch as a Hydrocolloid

 

Why is starch is the most important food thickener?

John Mitchell

 
Starch as a Hydrocolloid Why is starch is the most important food thickener? John Mitchell John.Mitchell@biopolymersolutions.co.,uk

John.Mitchell@biopolymersolutions.co.,uk

  • The starch granule

 The starch granule  Gelatinisation and gelation: What is the difference?  Modified starches 
  • Gelatinisation and gelation: What is the difference?

  • Modified starches

  • What is the difference between starch and hydrocolloid solutions at the same viscosity

Size shape and morphology of the granules 10mm is characteristic of the botanical source shoti wheat
Size shape and morphology of the granules
10mm
is characteristic of the botanical source
shoti
wheat
lentil
potato
avacado
rice
green
rye
maize
pea

Amylose // amylopectin

Amylose

amylopectin contents

contents

Amylose // amylopectin Amylose amylopectin contents contents Starch Source % amylose % amylopectin Maize 26 76

Starch Source

% amylose

 

% amylopectin

 
   

Maize

26

76

Wheat

25

75

Potato

24

76

Tapioca

17

83

Rice

17

83

Waxy maize

<1

>99

High amylose

50

/ 75

50

/ 25

Amylose and Amylopectin Starch normally contains two polysaccharides amylose and amylopectin Amylose Almost entirely linear (α
Amylose and Amylopectin
Starch normally contains two
polysaccharides amylose and
amylopectin
Amylose
Almost entirely linear (α 1-4 linked)
Molecular size ~ 5. 10 5 g mol -1
Amylopectin
Highly branched (α 1-4 and α 1-4 linkages)
Molecular size ~ 10 8 g mol -1
Amylopectin Racemose model Glucose units linked 1-4 and some  1-6 linkage 70-99% by weight Mol
Amylopectin
Racemose model
Glucose units linked 1-4
and
some  1-6 linkage
70-99% by weight
Mol weight ----10 8 g mol -1
branch chains
~20 glucose units
only one reducing end
Diagram of the starch polymer organisation
Diagram of the starch polymer organisation
Packing of the molecules to form a starch granule lamellae Jenkins and Donald, 1995 growth ring
Packing of the molecules to form a starch granule
lamellae
Jenkins and Donald, 1995
growth ring
Gelatinisation vs Gelation

Gelatinisation vs Gelation

Gelatinisation

Gelatinisation  Description of structural transformation which occurs when starch granules are heated in excess water
  • Description of structural transformation which occurs when starch granules are heated in excess water

    • Swelling of starch granules

    • Increase in viscosity

    • Loss of birefringence (maltese cross pattern seen under polarising microscope)

    • Accompanied by heat adsorption as seen by endotherm in differential scanning calorimetry

    • Occurs in temperature range ~55-75 O C as measured by loss of birefringence (high amylose starches higher)

Gelation

Gelation  Formation of crosslinked network on cooling as a result of formation amylose double helices
  • Formation of crosslinked network on cooling as a result of formation amylose double helices

  • Individual polysacchardies

    • Amylose forms “strong gels rapidly at minimum concentrations ~2%.

    • Amylopectin forms weak gels slowly much higher concentrations required (~20%)

Electron Micrograph Showing Structure of an Amylose Gel

Electron Micrograph Showing Structure of an Amylose Gel
Modified Starches

Modified Starches

Modified starch

Modified

starch ee numbers

numbers

  • E 1404 oxidised starch

  • E 1410 monostarch phosphate

  • E 1412 distarch phosphate

Modified starch Modified starch ee numbers numbers  E 1404 oxidised starch  E 1410 monostarch
  • E 1413 phosphated distarch phosphate

  • E 1414 acetylated distarch phpsphate

  • E 1420 acetylated starch

  • E 1422 acetylated distarch adipate

  • E 1440 hydroxypropyl starch

  • E 1442 hydroxypropyl distarch phosphate

  • E 1451 acetylated oxidised starch

  • E 1450 Starch sodium octenyl succinate

Acid thinned starches like unmodified starches are deemed to be ingredients NOT additives

Properties of

Properties

of native

native starches

starches

Starch

Granule

Gel Temp

Solution

Gel

Stability to

Resistance

Freeze /

Source

Size m.

o C

Clarity

Texture

retrogradn.

to shear

thaw

stability

Maize

10

- 20

- 74

  • 62 Short

Opaque

 

Poor

Fair

Poor

Wheat

A 25 –35 B 2 -5

– 64

  • 52 Short

Opaque

 

Poor

Fair

Poor

Rice

3

- 8

– 78

  • 61 Short

Opaque

 

Poor

Fair

Poor

Potato

15

- 100

– 69

Clear

  • 56 Very

Cohesive

Fair

Poor

Poor

Tapioca

20

- 60

- 72

  • 60 Soft

Clear

 

Fair

Poor

Poor

Sago

15

- 25

– 64

  • 52 Soft

Clear

 

Fair

Poor

Poor

Waxy

6

- 30

- 72

  • 63 Cohesive

Clear

 

Good

Poor

Fair

Maize

Chemical Chemical Modification Modification Modification Reagent Product Acid Thinning Oxidation Cross linking Hydrochloric acid Sodium hypochlorite
Chemical
Chemical Modification
Modification
Modification
Reagent
Product
Acid Thinning
Oxidation
Cross linking
Hydrochloric acid
Sodium hypochlorite
Phosphorus
oxychloride
Acid thinned starch
Oxidised starch
Distarch phosphate
Sod. Tri meta
phosphate
Distarch phosphate
Adipic anhydride
Epichlorohydrin
Distarch adipate
Distarch glycerol
Esterification
Etherification
Acetic anhydride
Propylene oxide
Starch acetate
PO starch ester

Effect of

Effect

of Cross

Cross linking

linking onon Brabender

Brabender

Viscosity

Viscosity

Effect of Effect of Cross Cross linking linking onon Brabender Brabender Viscosity Viscosity Viscosity 0.03% POCl

Viscosity

Effect of Effect of Cross Cross linking linking onon Brabender Brabender Viscosity Viscosity Viscosity 0.03% POCl

0.03% POCl 3

0.05% POCl 3

0.075% POCl 3 Control

0.15% POCl 3

0

95

95

50

Temperature o C

What is the difference between starch and hydrocolloid “solutions” at the same viscosity ?

What is the difference between starch and hydrocolloid “solutions” at the same viscosity ?

Solutions can be thickened with swollen particles or polymers in solution

Solutions can be thickened with swollen particles or polymers in solution Swollen starch granules Plant cells
Solutions can be thickened with swollen particles or polymers in solution Swollen starch granules Plant cells

Swollen starch granules Plant cells Gel particles

Solutions can be thickened with swollen particles or polymers in solution Swollen starch granules Plant cells

Guar gum Pectin Hydroxypropylcellulose

 The next slide shows the appearance of a predominantly paticulate suspension (wheat starch) and a
  • The next slide shows the appearance of a predominantly paticulate suspension (wheat starch) and a polymer solution (hydroxpropylmethylcellulose

(HPMC)) which have been stained with a red food

dye and gently hand mixed with water. mixing the viscosity of the stained

Prior to

suspension/solution was 380mPa.s at ambient temperature and a 50s -1.

  • In contrast to wheat, waxy maize starch which contains no amylose will disrupt on gelatinisation behaving more like a polymer solution than a suspension of particles. The modified waxy maize starch maintains the particulate structure .

Five Minutes After Mixing

Native Waxy Maize Starch HPMC
Native
Waxy
Maize
Starch
HPMC
Five Minutes After Mixing Native Waxy Maize Starch HPMC Wheat Starch Modified Waxy Maize Starch

Wheat

Starch

Modified

Waxy

Maize

Starch

Consequence of Good Mixing of Solutions Thickened by Swollen Starches

  • Good taste perception

  • Short non-stringy texture

Consequence of Good Mixing of Solutions Thickened by Swollen Starches  Good taste perception  Short
  • Longer gastric emptying time

Perceived Flavour Plotted Against Kokini Shear Stress 2.1 2 w axy maize (crosslinked) w heat 1.9
Perceived Flavour Plotted Against Kokini
Shear Stress
2.1
2
w axy maize
(crosslinked)
w heat
1.9
1.8
1.7
w axy maize
native
HPMC (Anne-
Laure)
HPMC (Dave
Cook)
1.6
1.5
-0.25
0.25
0.75
1.25
1.75
log (Kokini shear stress (Pa))
log (mean flavour )

Mouthfeel of Hydrocolloid Solutions (Szcznesniak

and Farkas (1962), Mitchell (1979))

Most Slimy Least Slimy
Most Slimy
Least Slimy
Mouthfeel of Hydrocolloid Solutions (Szcznesniak and Farkas (1962 ) , Mitchell (1979)) Most Slimy Least Slimy

Slimy material

Mouthfeel of Hydrocolloid Solutions (Szcznesniak and Farkas (1962 ) , Mitchell (1979)) Most Slimy Least Slimy

thick, coats the mouth and is difficult to swallow

Effects in the stomach (b) (a) STOMACH CONTENTS LIVER SPINE • fully mixed SPLEEN • longer
Effects in the stomach
(b)
(a)
STOMACH CONTENTS
LIVER
SPINE
• fully mixed
SPLEEN
• longer gastric emptying time
• some remains unmixed

MRI pictures of stomach content following the ingestion of 400g of water and 100g of

(a)a crosslinked waxy maize starch and

(b)

HPMC equivalent viscosity of 500mPa.s at 50s -1 .

at an

Acknowledgements: L. Marciani

Consequences of changing microstructure of starch

Consequences of changing microstructure of starch Origin of Starch Waxy maize (100% amylopectin) Waxy maize physically
Consequences of changing microstructure of starch Origin of Starch Waxy maize (100% amylopectin) Waxy maize physically

Origin of Starch

Consequences of changing microstructure of starch Origin of Starch Waxy maize (100% amylopectin) Waxy maize physically

Waxy maize (100% amylopectin)

Consequences of changing microstructure of starch Origin of Starch Waxy maize (100% amylopectin) Waxy maize physically

Waxy maize physically treated to prevent granule break up

Wheat

Salivary amylase

Effect of processing, origin and amylase on microstructure of paste

Processing

Heat shear
Heat
shear

Swelling

Polysaccharide released from swollen granule

Effect of processing, origin and amylase on microstructure of paste Processing Heat shear Swelling Polysaccharide released
Effect of processing, origin and amylase on microstructure of paste Processing Heat shear Swelling Polysaccharide released
Granule disruption
Granule
disruption

Botanical

Salivary

origin

amylase

Modified/crosslinked waxy maize

Wheat

Native

waxy

maize

starch

Effect of processing, origin and amylase on microstructure of paste Processing Heat shear Swelling Polysaccharide released

Cooked starch

Cooked

starch Characteristics

Characteristics

Cooked starch Cooked starch Characteristics Characteristics
 

Undercooked

Undercooked

Optimal

Optimal

cooking

cooking

Overcooked

Overcooked

   

Appearance

Cloudy

Clear

Clear

Texture

Thin, starchy

Heavy bodied,

Cohesive, long

taste

short textured

texture

Stability

Poor

Good

Many

fragments, few

intact granules

Viscosity

Low

Good

Viscosity drop

Microscope

Small granules,

Well swollen,

Many

under swollen,

some

fragments,few

birefingent

fragments

intact granules

cross

Consequences of changing microstructure of starch

Consequences of changing microstructure of starch
Consequences of changing microstructure of starch
Consequences of changing microstructure of starch
Consequences of changing microstructure of starch

Starch systems – impact of

origin

Starch systems – impact of origin  Wheat – Modified waxy maize give higher mixing efficiency
  • Wheat – Modified waxy maize give higher mixing efficiency / sodium release / taste perception than non-modified waxy maize

Wheat Waxy maize Modified waxy maize 100 μm 100 μm 100 μm
Wheat
Waxy maize
Modified waxy maize
100 μm
100 μm
100 μm

Starch systems – impact of

salivary amylase

Starch systems – impact of salivary amylase  α - amylase is an enzyme present in
  • α-amylase is an enzyme present in saliva, can cleave α 1-4 bonds between glucose

residues in starch molecules

  • At the concentrations present in saliva it can

halve the viscosity of a starch paste in a few

seconds

  • Large variation in in-mouth amylase activity between subjects

Starch systems – impact of salivary amylase 0 50 100 150 200 Waxy maize starch Modified

Starch systems – impact of

salivary amylase

0
0
50
50
100
100
150 200
150
200

Waxy maize starch

Modified waxy maize starch

0 50 100 150 200 0 50 100 100 μm
0
50
100
150
200
0
50
100
100 μm
2-a 100 μm
2-a
100 μm
50
50
100
100

Correlations between perceived saltiness and thickness and panellists saliva amylase activity

Correlations between perceived saltiness and thickness and panellists saliva amylase activity Thickener type Saltiness Thickness HPMC

Thickener type

Saltiness

Thickness

HPMC

0.11ns

0.09ns

Waxy maize starch

-0.20*

-0.28***

Modified waxy maize starch

-0.43***

-0.19*

Wheat starch

-0.25***

-0.14ns

Conclusions from amylase

study

Conclusions from amylase study  Amylase activity in the mouth releases polymeric material from swollen starch
  • Amylase activity in the mouth releases polymeric material from swollen starch granules reducing mixing efficiency and salt perception

  • Data suggests that consumers who have a high in-mouth amylase activity perceive flavour/taste in starch thickened foods less well

The Weakest Link?

Microstructure

Rheology

The Weakest Link? Microstructure Rheology Mixing Sensory/in body performance

Mixing

The Weakest Link? Microstructure Rheology Mixing Sensory/in body performance

Sensory/in

body

performance

The Weakest Link? Microstructure Rheology Mixing Sensory/in body performance

Observation of droplet break up in two fluid systems

Observation of droplet break up in two fluid systems  Easy break up of the viscous
  • Easy break up of the viscous fluid element will result in good mixing

    • Rheooptics

    • CaBER rheometer

Counter rotating shear cell 1: Transparent parallel rotating Silicon oil 2 plates. 1 V F G
Counter rotating shear cell
1: Transparent parallel rotating
Silicon oil
2
plates.
1
V
F
G
2: Observed object in suspending
fluid
3: Image acquisition unit: optical
microscope +camera+ monitor +
DVD recorder
Fluid droplet
3
  • - 2 transparent plates rotating in opposite directions

Counter rotating shear cell 1: Transparent parallel rotating Silicon oil 2 plates. 1 V F G
  • - Gap (h) is 1mm, radius (r) at which the droplet sits 5-10mm

  • - droplet is submitted to a known shear rate calculated as follows:

u

*

l

r

h

with ω u and ω l the relative velocities of upper and lower plate respectively

  • - Suspending fluid: high viscosity silicon oil (transparent, inert towards aqueous systems, induces high stresses)

Counter rotating shear cell 1: Transparent parallel rotating Silicon oil 2 plates. 1 V F G

Observed system is static in laboratory reference

HPMC and cross linked waxy maize starch at equivalent shear viscosities 3 0 50 100 150

HPMC and cross linked waxy maize starch at equivalent shear viscosities

3 0 50 100 150 250 300 200 0 1 2 CLWM 4 5 6 7
3
0
50
100
150
250
300
200
0
1
2
CLWM
4
5
6
7
L/Do
HPMC overshoot, no break
Starch deformation and break
up
up
HPMC

Strain

HPMC

100µ 100µm m
100µ
100µm
m
CLWM 100µm
CLWM
100µm

HPMC and CLWM at shear stress 640Pa. D 0 =80μm

Under the same conditions, HPMC and CLWM behave differently; - HPMC reaches a steady-state deformation - CLWM deforms and breaks up.

CaBER Extensional Rheometer

CaBER Extensional Rheometer
CaBER Extensional Rheometer
CaBER Extensional Rheometer

Experimental Conditions

Experimental Conditions  The sample is placed between two parallel plate (6mm diameter) separated by a
  • The sample is placed between two parallel plate (6mm diameter) separated by a 3mm gap.

  • The fluid is then exposed to a rapid extensional step strain by moving the upper plate upwards (final gap 11.3mm, linear strike, 50ms), thereby forming a fluid filament.

  • A laser micrometer measures the midpoint diameter of the gradually thinning fluid filament, after the upper plate has reached its final position, until its break-up.

Break-up time (s.)

Filament break-up times for good mixers

0.05

   

0.04

 
0.04 Processed xanthan

Processed xanthan

 

0.03

 
0.03 Waxy maize

Waxy maize

 

0.02

 

0.01

 
0.01 Wheat

Wheat

 
 

Gelatine

M odified waxy maize

0.00

0.2

0.3

0.4

0.00 0.2 0.3 0.4 0.5 0.6

0.5

0.6

Break-up time (s.) Filament break-up times for good mixers 0.05 0.04 Processed xanthan 0.03 Waxy maize

Viscosity 50s -1 (Pa.s)

Perceived Flavour Plotted Against Kokini Shear Stress 2.1 2 w axy maize (crosslinked) w heat 1.9
Perceived Flavour Plotted Against Kokini
Shear Stress
2.1
2
w axy maize
(crosslinked)
w heat
1.9
1.8
1.7
w axy maize
native
HPMC (Anne-
Laure)
HPMC (Dave
Cook)
1.6
1.5
-0.25
0.25
0.75
1.25
1.75
log (Kokini shear stress (Pa))
log (mean flavour )

Conclusion

Conclusion  As a thickener for foods starch has a fundamental advantage over most other polysaccharide
  • As a thickener for foods starch has a fundamental advantage over most other

polysaccharide hydrocolloids due to its more

efficient mixing with bodily fluids

Conclusion  As a thickener for foods starch has a fundamental advantage over most other polysaccharide

References

References Murphy, P and Mitchell, J, (2009) Starch in Handbook of Hydrocolloids edited and Phillips G.O

Murphy, P and Mitchell, J, (2009) Starch in Handbook of

Hydrocolloids edited and Phillips G.O and Williams P.A,

Woodhead Publishers

Ferry, A-L et al. Viscosity and flavour perception. Why is starch

different from hydrocolloids? Food Hydrocolloids (2006) 20:855

Ferry, A-L et al. In-mouth amylase activity can reduce perception

of saltiness in starch thickened foods. J of Agricultural and

Food Chemistry (2006) 54:8869

Desse, M, Wolf, B, Mitchell, J. and Budtova, T Experimental study

of the break up of starch suspension droplet in step-up shear

flow . J Rheology (2009) 53: 943

Thanks

Thanks  Ann-Laure Ferry (Nestlé, DEFRA Food Link)  Melinda Desse (European Polysaccharide Network of Excellence)
  • Ann-Laure Ferry (Nestlé, DEFRA Food Link)

  • Melinda Desse (European Polysaccharide Network of Excellence)

  • Bettina Wolf

  • Tatiana Budtova

  • Sandra Hill

  • Tim Foster

  • Luca Marciani

  • Andy Taylor

  • Dave Cook

  • Dave Howling

  • Margaret Hill