Der ganzheitliche Ansatz in der Produktentwicklung · Der ganzheitliche Ansatz in der...

Der ganzheitliche Ansatz in der

Produktentwicklung

Bildung von Karamell-Flavour

durch Extrusion

Imre BlankNestle PTC Orbe

IVV Jahrestagung, Freising, 4-5. Juni 2008

IVV meeting / June 6, 2008 / I. Blank 2

Flavour is one of the major drivers of consumer preference

However, there are many other factors of similar importance

Colour, shape, texture,

Nutritive value, safety, Convenience, packaging, …

Flavouring can be achieved by- Adding finished flavours,

- Generating flavours upon food processing, e.g. extrusion

Louis-Leopold Boilly, Les Cinq Sens (The Five Senses), 1823.


Flavour generation upon extrusion

Extrusion� Heat load (T, t)� Screw speed, SME� Moisture� Number of barrels � Slurry vs. dry addition� …

Recipe� Ingredients� Specific precursors� Concentration, ratio� Catalyst� pH� …

Highly complex system 1. Model productManifold interactions & variability 2. Target product

Effects difficult to predict Systematic approach Experimental design

Product characterisation Sensory evaluationVolatiles/non-volatiles analysesChemical/physical measurements


Generation of caramel-type flavournotes upon extrusion

Objective:

� Identify conditions favouring the transformation of rhamnose into furaneol - a caramel-like smelling compound

� Extruded product: Effect of extrusion parameters and recipe composition on furaneol formation from rhamnose and lysine

Optimised recipe and processing conditions favouring the formation of caramel flavour upon extrusion of rice flour

NH2 OH

O

NH2 O

OHO

CH3

CH3

+Recipe/Process

parameters


� Odour and taste:

� Odour threshold:

� Formation:

� Properties:

Target compound: Furaneol(4-Hydroxy-2,5-dimethyl-3(2H)furanone)

• white to yellow powder

• sensitive to oxidation

� Key flavour: • Fruits strawberry and pineapple

• Roasted products coffee, almonds, cereals

• depending on pH

• 21-158 µg/kg water

O

OHO

CH3

CH3

• degradation of 6-deoxy-sugars

in the presence of amino acids

• fruity, caramelized, sweet


Thermally induced formation of furaneol from sugars & derivatives

O

OHO

CH3

CH3

Amadori compounds

CH2- NH-CH-COOH

C=O

(CH-OH)3

CH2-OH

R

Hexose phosphates

CHO

CH-OH

(CH-OH)3

CH2-O- P

Hexose sugars

CHO

CH-OH

(CH-OH)3

CH2-OH

6-Deoxyhexose

CHO

CH-OH

(CH-OH)3

CH3

Sugar fragments

C3 + C3

Strecker-assisted

chain elongation

C5 + C1


Experimental setup: Key product attributes

affected by recipe and extrusion parameters

Recipe parameters • pH

• Ratio Rha/Lys

• Phosphate

Extrusion parameters• Moisture levels

• Screw Speed

• Temperature

• Residence time

• Slurry vs. dry

Mixing

Extrusion

Drying

Milling

Final product

Product characterisation

• Texture

• Crispness

• Colour

• Flavour

• Acrylamide

• Starch degradation

• Granulometry

• Viscosity

• Sensory

Fractional factorial design:- 32 instead of 576 trials

Modelling furaneol yield & rhamnose degradation by estimating

- all main effects and

- two-factor interactions

of 3 recipe & 5 process parameters

500400300Screw speed (rpm)

150135120Temp. (°C)

0.1340.035PO4 (mol/kg)

232017Moisture (%)

SlurryDryAddition

75Barrel length

3:13:0Rha:Lys

7.76.4pH


Holistic approach: Analytical characterisation

of samples from experimental design

List of analysis:• Residual rhamnose (HPLC/DAD)

• Furaneol (GC/MS)

• Acrylamide (HPLC/MS)

• Chemical composition (NIR)

• Moisture (MNR)

• Molecular weight profile of starch (GFAS = Gel Filtration Analysis of Starch)

• Molecular weight profile of debranched starch (SEC = Size Exclusion

Chromatography)

• Molecular weight profile of proteins (HPSEC = High Performance Size

Exclusion Chromatography)

• Colour

• Viscosity (rheometer, RVA profile)

• Granulometry (laser diffraction)

• Texture (X-ray tomography)

• Porosity (cells size & cell walls distributions, degree of anisotropy)

• Crispiness (average drop off, force Max)

• Sensory evaluation

Flavour ⇔ Recipe/process parameters ⇔ Other key product attributes


• Trained panel (14 panelists)

• Product– Extruded powder (85%)

– Sugar (15%)

• Reconstitution– 12.4g product

– 100mL milk at 70°C

• 32 Products evaluated vs. reference

• Identification of statistically relevant

trends

Parameters units Low Medium High

pH 6.4 7.7

Rha:Lys 3:0 3:1

Phosphate mol/kg 0.035 0.134

Moisture % 17 20 23

Screw speed rpm 300 400 500

T °C 120 135 150

length barrel short long

Addition dry slurry

Sensory assessment: Reconstituted

products from experimental design

-6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6

tEasySwallow

aLump

tSmooth

Burnt

Nutty

aDark

Caramel

Toasted

Processy

Off

Overall

acid

WholeGrain

Mushroom

astringent

bitter

aftertaste

t1Thick

tThick

tFluffy

t1Wettability

tSemolina

Cooked

Milky

Rice

Vanilla

sweet

Range covered by A01-A32 (vs. REF)

Fla

vo

r

Textu

re &

Ap

peara

nce

Range of sensory attributes

Wide diversity of sensory perception


0

4

8

12

16

20

20 30 40 50 60 70 80 90 100

SME measured / Wh/kg

Fu

ran

eo

l d

ry /

mo

l%

Correlation matrixNo correlation between furaneol level and SME


Correlation matrix

Furaneol vs SME

SME measured

SME calculated

Visco5min

ViscoMax

ViscoMaxTime

Visco5/3min

L

ab

C

h

Rha extRha dry

Furaneol ext

Furaneol dry

0

4

8

12

16

20

20 30 40 50 60 70 80 90 100

SME measured (Wh/kg)

Fu

ran

eol d

ry (

mo

l%)

Acrylamide

SME is negatively

correlated with viscosity

Furaneol is positively

correlated with the

degradation of rhamnose

and colour development


Sensory evaluationLink between sensory data and SME or Furaneol

sweet

VanillaRice

Milky

Cooked

tSemolina

t1Wettability

tFluffy

tThick

t1Thick

aftertaste

bitter

astringent

Mushroom

WholeGrain

acid

Overall

OffProcessy

Toasted

Caramel

aDark

Nutty

Burnt

tSmooth

aLump

tEasySwallow

Furaneol

SME

� Furaneol is related to odour,

flavour, and taste attributes

High � caramel, bitter/astringent,

strong overall/aftertaste,

burnt/nutty/toasted and

dark color

Low � mild notes, sweet, vanilla,

milky, cooked, rice

� SME is related to texture and

appearance

High � smooth, easy to swallow

Low � thick, semolina, wetability


Furaneol formation Free AA, moisture, T and phosphate are most critical

-6 -4 -2 0 2 4 6

pH 6.4pH 7.7

Rha:Lys 3:0Rha:Lys 3:1

Phosphate 0.035 mol/kgPhosphate 0.134 mol/kg

17% H2O20% H2O23% H2O

300 1/min400 1/min500 1/min

120 °C-Long120 °C135 °C150 °C

DrySlurry

Furaneol ext / mol% Furaneol dry / mol% Conversion of rhamnose to furaneol can be modulated through

changes of extrusion and/or recipe parameters

-6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6

tEasySwallowaLump

tSmooth

BurntNutty

aDarkCaramelToasted

ProcessyOff

Overallacid

WholeGrainMushroomastringent

bitteraftertaste

t1ThicktThicktFluffy

t1WettabilitytSemolina

CookedMilkyRice

Vanillasweet


Fla

vo

r

Se

ns

ory

imp

ac

t

Enhanced with furaneol

Reduced with furaneol


Effect of recipe/extrusion parameters Furaneol vs SME

pH 6pH 7

Rha:Lys 3:0

Rha:Lys 3:1

Phosphate low

Phosphate high

17% H2O

20% H2O

23% H2O

300rpm

400rpm

500rpm

120°C-Long

120°C135°C

150°C

Dry

Slurry

-4

-3

-2

-1

0

1

2

3

4

-20 -15 -10 -5 0 5 10 15 20

SME-measured

%F

ura

ne

ol-

dry

Temperature affects

both furaneol and SME

Free amino acid and

phosphate affect

furaneol, but not SME

Moisture affects both

furaneol and SME


Colour generation

-6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6

tEasySwallowaLump

tSmooth

BurntNutty

aDark

CaramelToasted

ProcessyOff

Overallacid

WholeGrainMushroomastringent

bitteraftertaste

t1ThicktThicktFluffy

t1WettabilitytSemolina

CookedMilkyRice

Vanillasweet


Se

ns

ory

imp

ac

t

Colour range

Colour development through extrusionModulate colour in product through recipe

Browning reactions

-6 -4 -2 0 2 4 6

pH 6pH 7


Phosphate lowPhosphate high

17% H2O20% H2O23% H2O

300rpm400rpm500rpm

120°C-Long120°C135°C150°C

DrySlurry

Colour (C)

** Lysine

* High pH

Ke

y p

ara

me

ters

Light Dark

pH 6Rha/Lys 3:0

pH 7Rha/Lys 3:1


Acrylamide Temperature is most critical

-75 -50 -25 0 25 50 75

pH 6.4

pH 7.7

Rha:Lys 3:0

Rha:Lys 3:1

Phosphate 0.035 mol/kg

Phosphate 0.134 mol/kg

17% H2O

20% H2O

23% H2O

300 1/min

400 1/min

500 1/min

120 °C-Long

120 °C

135 °C

150 °C

Dry

Slurry

Acrylamide

-6 -4 -2 0 2 4 6

pH 6.4pH 7.7



17% H2O20% H2O23% H2O

300 1/min400 1/min500 1/min

120 °C-Long120 °C135 °C150 °C

DrySlurry

Furaneol ext / mol% Furaneol dry / mol%

17-235 ppb


SME Temperature, moisture, screw speed are most critical

-15 -10 -5 0 5 10 15

pH 6.4pH 7.7



17% H2O20% H2O23% H2O

300 1/min400 1/min500 1/min

120 °C-Long120 °C135 °C150 °C

DrySlurry

SME measured / Wh/kg SME calculated / Wh/kg

Higher SME is achieved with low

moisture, high screw speed, low

temperature and long extruder.

No effect of recipe parameters on SME


Structure and Texture Moisture and temperature are most critical

-1500 -1000 -500 0 500 1000 1500

pH 6.4pH 7.7



17% H2O20% H2O23% H2O

300 1/min400 1/min500 1/min

120 °C-Long120 °C135 °C150 °C

DrySlurry

Visco5min / mPas ViscoMax / mPas

-15 -10 -5 0 5 10 15

Cell walls / µm

Structure = f (SME)Texture = f (SME)


StructureWide variety of structures obtained

-20 -10 0 10 20


0.035 mol/kg PO40.134 mol/kg PO4

17% H2O20% H2O23% H2O

300 1/min400 1/min500 1/min

120 °C-Long120 °C135 °C150 °C

DrySlurry

Main effect

Cell walls (um)

0

200

400

600

800

1000

1200

70 75 80 85 90

Porosity (%)

Mean

cell s

ize (

um

)

12 mm


Long ChainDP~50

Short ChainDP~25

Rice Flour

Moisture % 8-13

Starch %d.b. 88-92

Total fibers %d.b. 0.3-1

Proteins %d.b. 6-9

Fat %d.b. 0.5-1

Ash %d.b. 0.3-1

A17

0

10

20

30

40

50

60

70

80

90

100

1000 10000 100000 1000000 10000000 100000000

Molecular weight

Ca

rbo

hy

dra

tes (

g/1

00g

)

Total Amylopectin Intermediate1

Intermediate2 Amylose

A31

0

10

20

30

40

50

60

70

80

90

100

1000 10000 100000 1000000 10000000 100000000

Molecular w eight

Ca

rbo

hy

dra

tes (

g/1

00g

)



A28

0

10

20

30

40

50

60

70

80

90

100

1000 10000 100000 1000000 10000000 100000000

Molecular w eight

Ca

rbo

hyd

rate

s (

g/1

00g

)



A04

0

10

20

30

40

50

60

70

80

90

100

1000 10000 100000 1000000 10000000 100000000

Molecular w eight

Carb

oh

yd

rate

s (

g/1

00

g)



Amylopectin

High MW

Am

ylo

pe

cti

n,

hig

h M

W I

nte

rme

dia

te d

ep

oly

me

rize

d

Lo

wM

W In

term

ed

iate

ge

ne

rate

d, a

mylo

se

co

ns

tan

t

Low MW

Amylose

SME 92 SME 35

Texture: Starch degradation Depolymerisation of amylopectin increases with SME


A17

0

10

20

30

40

50

60

70

80

90

100

1000 10000 100000 1000000 10000000 100000000

Molecular weight

Ca

rbo

hy

dra

tes (

g/1

00g

)



A31

0

10

20

30

40

50

60

70

80

90

100

1000 10000 100000 1000000 10000000 100000000

Molecular w eight

Ca

rbo

hy

dra

tes (

g/1

00g

)



A28

0

10

20

30

40

50

60

70

80

90

100

1000 10000 100000 1000000 10000000 100000000

Molecular w eight

Ca

rbo

hyd

rate

s (

g/1

00g

)



A04

0

10

20

30

40

50

60

70

80

90

100

1000 10000 100000 1000000 10000000 100000000

Molecular w eight

Carb

oh

yd

rate

s (

g/1

00

g)



Amylopectin

High MW

Am

ylo

pe

cti

n,

hig

h M

W I

nte

rme

dia

te d

ep

oly

me

rize

d

Lo

wM

W In

term

ed

iate

ge

ne

rate

d, a

mylo

se

co

ns

tan

t

Low MW

Amylose

SME 92 SME 35

0

20

40

60

80

100

0 50 100

SME

Sta

rch

(%

)

Amylopectin

High MW

intermediate

Low MW

intermediate

Starch degradation MW = f (SME)

0

1000

2000

3000

4000

5000

6000

0 2 4 6 8 10 12

Vis

co

sit

y (

mP

a.s

)

Time (min)

SM

E 9

2S

ME

35RVA 50°C, 50rpm

21g+170mL milk

Viscosity = f (MW)

High H2OHigh T

Low H2OLow T


Conclusions

Critical parameters for generation of furaneol from rhamnose during extrusion:

• Furaneol generation is affected both by recipe parameters (Lys, PO4) and

extrusion parameters (T, moisture)

• Recipe parameters permit furaneol modulation w/o impact on texture

• Lower pH will limit colour and acrylamide development w/o affecting furaneol

formation

• Addition of amino acid will enhance furaneol while limiting acrylamide formation

• Temperature and moisture affect both furaneol formation and texture (→ SME)

Full factorial design


� Hélène Chanvrier PTC Orbe Structure, texture

� Tomas Davidek PTC Orbe Flavour, acrylamide

� Valérie Leloup PTC Orbe Macromolecular chemistry

� Werner Pfaller PTC Orbe Extrusion

� Andreas Rytz NRC Lausanne Experimental design

� Silke Illmann Univ. Karlsruhe Diploma work

� Claudia Leeb Univ. Karlsruhe Extrusion

� Heike Schuchmann Univ. Karlsruhe Extrusion

Thanks to…

………… and to you for your kind attention !and to you for your kind attention !and to you for your kind attention !and to you for your kind attention !

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