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Trends in Understanding the Science &

Technology of Cocoa, Coffee, and Tea

2nd CoCoTea Conference, Naples, October 9-11, 2013 Imre Blank, Arne Glabasnia, and Andrew Scott

Nestlé R&D

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Technical challenges to meet consumers’ expectations

Nestle R&D / Imre Blank / 11.10.2013

All five senses are key for

consumer preference

• Raw material quality, sourcing

• Mild processing

• Desirable vs undesirable effects

• Industrial efficiency

• Products in various formats (powder, liquid)

• Product properties (e.g. wettability, flowability)

• Shelf life, freshness

• Products with multiple benefits: Aroma, taste,

colour, health benefits, powder properties

2

Global consumer mega-trends contributing

to quality of life


Well-being matters Achieve better performance To look good

Get and keep balance To stay free of diseases

Minimize the effect of ageing / prevent Less fat, sugar, salt The green season

Lifestyle Redefiniton

No time to sit down but want the experience

Easier, Faster and Disposable

Leave more time for work or leisure

Less hassle, no mess

Men and Women roles mixed

Slow Cooking made fast and easy

Satisfying the Senses

Guilt-free indulgence Emotional compensation for stress Mass - Luxury

Individualism - Homing Worldly tastes

Increased willingness to experiment with ethnic Artisanal varieties

(Source: Datamonitor, Reuters)

Convenience Pleasure Health

3

Chemic al composition of Cocoa, Coffee, and Tea


Content (% db) Arabica Robusta

Polysaccharides 48.5 46.3

Sucrose 7.6 4.6

Lipids 14.2 12.7

Trigonelline 0.9 0.7

Organic acids 2.3 1.6

Proteins 11.3 12.7

Caffeine 1.2 2.3

Chlorogenic acids 7.5 10.1

Ash 4.0 4.4

Average composition of green coffee

Component Content [% db]

Carbohydrates 25

Polyphenol 30

Protein 15

Amino acids 4

Methylxanthines 3.5

Lipids 2

Organic acids 1.5

Ash 5

Composition of fermented cocoa beans

Green tea leaf (Graham, 1992)

• Similarities: Polyphenols, methylxanthines

• Differences: Trigonellin (coffee), theanin (tea)

4

//upload.wikimedia.org/wikipedia/commons/c/cc/Trigonelline.png

//upload.wikimedia.org/wikipedia/commons/1/1b/Chlorogenic-acid-from-CAS-2D-skeletal.png

//upload.wikimedia.org/wikipedia/commons/0/0c/Methylxanthin_(R1,_R2,_R3).svg

(Poly)phenols

Flavanols

Isoflavones (genistein,

daidzein)

Flavonols (e.g. quercetin)

Anthocyanins

Catechins Pro(antho)cyanidins

Flavanones

e.g. hesperidin

Flavonoids

Phenolic acids (e.g ferulic

acid, caffeic acid,

chlorogenic acids)

Ellagic acid/ellagitannins

The family tree of (poly)phenols


Multiple role of polyphenols

in coffee, cocoa, and tea

driving quality attributes:

Aroma, taste, colour,

health benefits, texture

5

Diversity of chlorogenic acids in COFFEE


3-caffeoyl quinic acid 4-caffeoyl quinic acid 5-caffeoyl quinic acid

coumaric acid dimethoxycaffeic acid trimethoxycaffeic acid sinapic acid

RO

O

OH

RO

O

OH

OCH3

OCH3

RO

O

OCH3

OCH3

OCH3

RO

O

OCH3

OCH3

OH

O

OH

OH

O

OH

O

OH

OH

OH

OH

OH

O

O

OH

O

OH

OH

OH

OH

O

OH

O

OH O OH

OH

3-feruoyl quinic acid 4-feruoyl quinic acid 5-feruoyl quinic acid

OH

O

OH

OH

O

OH

O

OH

H3CO

OH

OH

OH

O

O

OH

O

OH

OCH3

OH

OH

O

OH

O

OH O OH

OCH3

6

Chlorogenic acids as quality markers for green coffee

• To differentiate between Robusta and Arabica

• To calculate blend of unknown samples

– by NIR (Haiduc et al.)

– by NMR (Wei et al. 2010)

– by LC/MS direct infusion (Garrett et al. 2012)


Arabica

Robusta

(Haiduc et al, unpublished) (Garrett et al, 2012)

Blend

Post harvest

Cultivar

Crop

7

Transformation of raw materials: Chemical & physical

changes upon roasting of green coffee beans

Lipids

Amino acids

& Proteins

Sugar -

Carbohydrates

yyyy-mm-ddNRC/dpt - name/ 12

NRC Nestlé Research Center

Arabinogalactan-Protein Structure

O

OOH

OH

CH2OH

O

O

OH

OH

OHOOH

OH

CH2OH

O

OOH

OH

OH

CH2OH

OOH

OH

CH2

O OOOH

H2C

OOOH

OH

CH2OH

OOOH

OH

OH

H2C

OOH

OH

OH

CH2OH

O

OOH

OH

OH

CH2

O

OH

Protein

Arabinogalactan

Polyphenols (CAs)

Aroma, Taste,

Colour, Health

benefits

Roasting

Key reactions:

• Maillard reaction

• Lipid oxidation

• Radical induced

conversion of phenols

20 10 15 0 5

60

80

100

40

0

20

Roasting losses (%)

% d

eg

rad

ed

1- Sucrose

2- CAs

Trigonelline

3- Proteins

Polysaccharides

Nestle R&D / Imre Blank / 11.10.2013 8

HTKZ_mpeg4v2_15fr.avi


Chlorogenic acids as aroma precursors upon roasting

9


Formation of coffee aroma compounds upon roasting

phenolic aroma

compounds

Robusta green beans (9.2%)

contain more chlorogenic

acids than Arabica (7.2%)

Kinetics of degradation of precursors

(amino acids) and formation of aroma

compounds correspond quite well

(Wocheslander et al, unpublished)

10

Formation of bitter tastants upon coffee roasting


0

20

40

60

80

100

120

green 110 90 70 50

Rel%

Roast degree

Caffeine CQL DKP Phenylindane• Bitter precursor content

depends on blend

• Bitter compound formation

depends on roasting degree

• Kinetics are different for

different chemical classes

• Bitter quality also different

coffee-like

harsh

caffeine-like

metallic

Compound

class

Threshold for

bitterness (μmol/L)

Caffeine 750

Lactones 30-200

DKPs 190-4000

Phenylindanes 30-150

Benzenediols 100-800

(Frank et al, 2006-2007) O

OH

OH

11

//upload.wikimedia.org/wikipedia/commons/5/5e/Caffeine-2D-skeletal.svg

//upload.wikimedia.org/wikipedia/commons/3/36/Diketopiperazine.png

Sensory-analytical correlation: Around 30 compounds

exhibit strong correlation to the sensory descriptors

sweet

roasty

dry vegetal

cocoa

bitter

vegetal-humus

green vegetal

acid

fruity-flowery

2-acetylpyridine

pyridine furfuryl acetate

phenylacetaldehyde

3-methyl-2-butene-

thiol

N-methylpyrrole

2-isopropyl-3-methoxypyrazine

2-methyl-3-furanthiol

4-ethylguaiacol

guaiacol

4-vinylguaiacol

dimethyl trisulfide

2,3-diethyl-5-methylpyrazine p-cresol

2-isobutyl-3-methoxypyrazine

2-methylpropanal

vanilline

2-acetylthiazole

hexanal

2-methylbutanal

methional

furfural

sotolon

furaneol

2,3-pentanedione

dimethyl sulfide

2,3,5-trimethylpyrazine

2-furfurylthiol

acetaldehyde

methanethiol

2,3-butanedione

Correlation found for aroma

compounds derived from CQA

breakdown with bitterness

perception


(Baggenstoss et al, ASIC 2010)

12

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Bitterness prediction model from aroma compounds

including those derived from CQA is very good


(Baggenstoss et al, ASIC 2010)

13

16 17


Effect of roasting conditions on taste formation

Percolation of roast & ground coffee with hot water 4-V

inylc

ate

ch

ol

oli

go

mers

(260°C)

4-Vinylcatechol oligomers

Strong retention to

the coffee material

(Blumberg et al, 2010)

14

What matters in COCOA powder?

Health Benefits

Healthy growth Balanced

nutrition

Appearance Taste & Texture

One of the most complex

flavours known to mankind

Up to 20 chemical classes

involved (Schieberle et al,

Hofmann et al)

Fibres:

Cellulose

Pectin

Colour

Wettability

CVD Cognition

Skin Health Metabolic Health Immune function

Increasing number of scientific

publication on cocoa covering a

large range of health benefits

cocoa

astringent

bitter

acid

smokey

fruity

roasted

Appearance Flavour


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Polyphenols in Cocoa

(Ferruzzi et al., 2012)

16

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Impact of processing on bioactive compounds and colour

formation

0.E+00

1.E+07

2.E+07

3.E+07

4.E+07

5.E+07

Theobromine

0.E+00

5.E+04

1.E+05

2.E+05

2.E+05

3.E+05

3.E+05

4.E+05Pro-Val

0.E+00

2.E+05

4.E+05

6.E+05

8.E+05

1.E+06

1.E+06

1.E+06

2.E+06catechin

More red

Mo

re d

ark


0.E+00

2.E+05

4.E+05

6.E+05

8.E+05

1.E+06

1.E+06

Tyrosin

17

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Is pH related to the chemical diversity of cocoa powders?

< pH 6.0 (natural cocoa)

pH 6.5 - 6.9

pH 7.0 – 7.4

pH 7.5 – 7.9 > pH 8.0

pH 6.0 – 6.4

-0.00014

-0.00012

-0.00010

-0.00008

-0.00006

-0.00004

-0.00002

0.00000

0.00002

0.00004

0.00006

0.00008

0.00010

0.00012

0.00014

-0.00020 -0.00015 -0.00010 -0.00005 0.00000 0.00005 0.00010 0.00015 0.00020

t[2]

t[1]

TotalCocoa_Chained-Filters.M3 (PCA-X), 10-12

t[Comp. 1]/t[Comp. 2]

Colored according to Obs ID (pH range)

R2X[1] = 0.646415 R2X[2] = 0.249284

Ellipse: Hotelling T2 (0.95)

No ID

0

1

3

4

5

6

11-D-040

N11N

D102C

D11MA

JB350-11JB310-11

D11 VB

DR74

DR79

DF700-11BRD11SB

D11 CE

GT 150

D11RB

SamaraSamara

DSR

GT78

D11DQ

10 12 DZA

200 DP11

250 DP 11

SR7

SR4

D11A

Valencia

DP

JB200-11

Impact-AL7

DP70

AJ11MV

354 DP 11

10-12 MR

DCP 10 R 1

GT50

DE 7800-11

DF7160-11

354 DP 11

Marquise R

AJ11V

1012 RB

D11S

DB82

DF 7150-11

SR8

SR5

D11CA

SIMCA-P+ 12.0.1 - 2012-03-23 13:27:08 (UTC+1) pH (alkali concentration) does not explain alone

chemical diversity. Additional parameter may be:

Roasting

Bean origin


Caking of cocoa powder: Water a major food

plasticizer

1.E+01

1.E+02

1.E+03

1.E+04

1.E+05

Ref 10% 30%T

ota

l E

nerg

y (

g.m

m)


Failure test (force vs. distance)

Texture Analyser distance= 10mm, speed= 0.1 mm/s

19

Consumer trend: Reduced-fat chocolate

Chocolate is considered to be an

indulgent product and consumers

not willing to sacrifice taste.

Euromonitor valued the global

reduced fat chocolate market at

$440m in 2012 and it is forecasting

13.4% growth this year (US: 80%) Effect of Fat content on Consumer preference


Fat reduction significantly increases chocolate viscosity

1 Do, T-A L et al, J Food Sci, 72(9), 541-52, 2007

• Viscosity increases as fat content is

reduced from 35% fat suspension

• Chocolate viscosity increases

significantly below 28% fat.

• The rheological properties of molten

chocolate influence the eating

experience of chocolate

• Fat plays an important role in the chocolate

mouthfeel

• The way fat melts in mouth has profound

impact in “mouthfeel” of chocolate

• Understand processes and driving factors

controlling in-mouth texture of chocolate to

achieve enjoyment at lower levels of fat


Viscosity reduction by lowering inter-particle interaction,

aggregation during flow

Surfactants play important role in achieving desired flow properties of chocolate (Do et al, 2010)


Limonene

Triglyceride

Effect of limonene on viscosity of

reduced-fat chocolate (25%fat)

Limonene mixes with and within the cocoa

butter TAGs, diluting the fat and leading to

a decrease in overall fat viscosity (EP0898897) 22

Andrew Scott Nestle R&D / Imre Blank / 11.10.2013

Polyphenols in TEA

23

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24

Polyphenol composition and tea processing


White tea

Buds &

young leaves

Sun & air

dried Dried

Green tea

Buds & young /

mature leaves

Withered Dried Steam or Pan-fried

(oxidase inactived)

Oolong tea Withered Dried Pan-fried Buds & young /

mature leaves

Bruised Partially

oxidised

(fermented)

Black tea Withered Dried Oven

dried /

fired

Buds & young /

mature leaves

Rolled /

Cut, tea

& curl)

Extensively

oxidised

(fermented) Catechins Theaflavins &

thearubigens

oxidation

(fermentation) oxidation

(fermentation)

ΔT / ox. ΔT / ox.

Tea polyphenols: Composition, Taste and Brewing

0

2

4

6

8

10

12

14

16

% d

mb

Average content of selected compounds in green and black tea

green black

0

10

20

30

40

50

60

70

80

90

100 95

45

34

73

6370

59

49%

2 min aq brews vs total – Black teabags


Polyphenol

Taste

Threshold

(μmol; water)

Flavan-3-ols

„astringent“

190-930

Theaflavins

Mouth-drying, rough

13-26

Flavonol glycosides

Velvety, silky astringent

mouth-coating

0.001 – 20 0

100

200

300

400

500

600

700

800

900

1000

Compound

Astringency (molar base)

Rutin

(Engelhard et al., 2000)

(Scharbert et al., 2004) 25

Conclusions

• Composition of the raw material is key to product quality, along with

(mild) processing conditions

• Polyphenol chemistry is to be better understood to achieve multiple

benefits in the final product

• Targeted and holistic approaches are equally important (systemic

approach for multiple benefits), requires interdisciplinary thinking !

• Opportunities to leverage knowledge across product categories to be

explored more


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