Maillard 2

Flavor Compounds Formation by Maillard Reaction

Köln

Natural Flavour FormationNatural Flavour Formation

Biogenetic Flavours (Primary) Prepared Flavours (Secondary)(uncooked Food)

e. g. Milk Boiling Baking Broiling Roasting FermentationVegetable e.g. Potatoes Bread Meat Meat YoghurtFruits Vegetables Pastry Fish Coffee CheeseSpices Cereals Confectionery Potatoes Peanuts Pickled cabbage

Enzymatic Flavour Flavour Development Through MicrobiologicalDevelopment Heat-Treatment (e. g. Maillard-Reaction) Flavour Development

Flavor -Generation by Maillard –reaction: Heating up of Amino-Flavor -Generation by Maillard –reaction: Heating up of Amino-acids in the presence of Glucose (Rohan, 1999) acids in the presence of Glucose (Rohan, 1999)

Aminosäure /aminoacid Flavor/ Reaktionsaroma (sensorischer Eindruck)100° C 180° C

Asparaginsäure Candy Karamel

Threonin Schokolade angebrannt

Serin Ahorn Sirup --

Glutaminsäure Karamel angebrannter Zucker

Prolin verbranntes Eiweiß Breadflavor

Glycin Karamel angebrannter Zucker

Alanin Karamel angebrannter Zucker

Valin Rye-Bread Schokolade (penetrant)

Ornithin Wheat bread Brot-flavor

Isoleucin muffig, fruchtig, aromatisch angebrannter Käse

Leucin Schokolade angebrannter Käse

Tyrosin Róse, Parfüm, Karamel Veilchen, Flieder

Lysin -- Bread

Histidin -- Maisbrot butterartig

Arginin butterartig verbrannter Zucker

Chemistry of Flavor Precursors

Flavor derived from carbohydrate and proteins

N

N CH3

N

CH3

N

CH3

S

R CH2

O

Furan Pyrrole Thiophene

Pyridine Pyrazine


Reducing Sugars and -amino acids

N-glycosylamine or N-fructosylamine

1-Amino-1-deoxy-2-ketose (Amadori intermediate) or 2-Amino-2-deoxy-1-aldose (Heynes intermediate)

Reductones and Dehydroreductones

Furans ThiophenesPyrroles

Retroaldol ReactionH2S

NH3

Strecker degradation

Amino Acids

Hydroxyacetone HydroxyacetylaldehydeAcetoinAcetylaldehyde

Glyoxal Pyruvaldehyde Glycerolaldehyde

Strecker Aldehydes +

CO2 + -aminoketone

(Methional, NH3, H2S)

HeterocyclizaionPyrazinesPyridinesOxazoles

ThiazolesPyrroles

++

Maillard Reaction-- Amadori Rearrangement

Imine Compound

- H2O

Amadori Rearrangement

- H2O

CH2OH

C O

CHOH

R

H2NR+

CH2OH

C

CHOH

R

NHROH H

COH

C

CHOH

R

NHR_

H2O

2-amino-2-deoxy-1-aldose

Maillard Reaction--Heynes Rearrangement

Heynes Rearrangement








NH3


Amino Acids




CO2 + -aminoketone



ThiazolesPyrroles

++

Amadori Intermediate Transformation for Reductones and Dehydroreductones Formation

1-amino-1-deoxy-2-ketose

H2C

CHOH

CHOH

C

NHR

O

R

H2C

CHOH

COH

COH

NHR

R

2,3-enediol

- NH R

CHOH

C

C

CH2

O

O

R

COH

COH

C

CH3

O

R

DEHYDROREDUCTONE REDUCTONE

K E

K E

Keto enolization

(Amadori rearrangement)

H

H

Keto enolization

1,4-Dideoxyhexasone from Amadori Product

Dehydroreductonefrom Amadori

CHOH

C

C

CH3

O

O

CHOH

CH2OH

_ H2O

CH

C

C O

O

COH

CH

C

C O

O

C O

Ketone formation

CH2

C

C O

O

C

CHOH

OH

CH2

C

C O

O

HC

C

OH

O

Enolization

1,4-dideoxyhexone

H

CH3 CH3

CH2OH CH2OH

CH3

CH3

H








NH3


Amino Acids




CO2 + -aminoketone



ThiazolesPyrroles

++

Aldol Condensation and Retro-Aldol Reaction

-hydroxy aldehyde is rather unstable and is easily dehydrated to compounds in which the double bond is conjugated with the carbonyl group

HC

C

CH2

O

O

CHOH

CHOH

CH2OH

3-deoxyhexosone

HC

C

CH 2

O

O

CHO

CHOH

+

Pyruvic aldehyde

Glycer-aldehyde

C O

CH2OH

H2O

H2O

CHO

C O

+

_

Pyruvic aldehyde

Dihydroxy acetone

Retro-Aldo Reaction

AldehydeAlcohol

CH2OH

CH2OH CH3

H

Retro-Aldol Reaction of Deoxyhexosones

1,4-dideoxyhexosone

CH3

C

C

CH2

CHOH

COH

O

O

CHO

CHO

CH3

C O

C O

CH3

Glyoxal

diacetyl

+Retro-Aldol Reaction

Aldol Condensation








NH3


Amino Acids




CO2 + -aminoketone



ThiazolesPyrroles

++

Hydroxymethylfural and Furfural

O CHOOH

H2COH O CHO

Dehydroreductone from hexose

_ HOH

_

O CHOO CHOOH

Dehydroreductone from pentose

5-hydroxymethylfurfural

Furfural

CHO

C=OCH

CH

CHOH

CH2OH

CHO

C=OCH

CH

CH2OH

H2COH

H2O

H

H

O CH3

OHO

OHH

3

2

- H O

O CH3

OHO

Cyclorization

5-methyl-4-hydroxy-3-(2H)-furanone (nor-furaneol)

HOH2C COOH

O

OH

OH

OH

5-ketogluconic acid

5-Methyl-4-Hydroxy-3(2H)-Furanone

-2H2O

-CO2

3

2

H

CH3

C O

COH

COH

CH2OH

Ketonization

CH3

C O

CHOH

C

CH2OH

O

2

3

5

4

Reductone from pentose

OH-

NCHO

R'

R

C

C O

HC

HC

H C

R

O

OH

H

+ R’NH2

C

C O

HC

HC

H C

R

O

NHR'

H

- H2O

-H2O

- H2O

C

C O

HC

HC

H C

R

O

N ‘R

H

H

Formyl Pyrrol Formation

'

Reductone(Rhamnose)

Isomaltol

-

O

OH

CH3

O

CH3

H2O

2

O

OH

OHO

CH3 CH3

34

CH3

C O

C

C

CHOH

CH3

O

6

5

4

2

3

1 CH3

C O

C

COH

CHOH

CH3

OH HOH

5

2,5-Dimethyl-4-Hydroxy-3-Furanone (Isomaltol)

CH3CH2 C

CHO

O

O

HOOCC O

CH3

+

CH3CH C

CHO

O

O

CHOOCCH3 OH

- HO

OO

OCH3

CH3

HOOC

OO

OCH3

CH3O

O

OHCH3

CH3

Maple Lactone

Ketobutyric acid

Maple Lactone Formation

- CO2

H








NH3


Amino Acids




CO2 + -aminoketone



ThiazolesPyrroles

++

R

C O

C O

R

Dicarbonyl

+ HN CH COOH

R1

2

3 3

2R

C

C O

R

HOH2N CH COOH

R1

Amino acid

- H2O

R

C

C O

R

2

3

CH COOH

R1

N

Schiff Base(imine)

CO2 N

H

CH

R1

3

2R

C

C O

R

-+

.

R

C

C O

R

N CH

R1

H

2

3

+ H2O R1 CHO

3

2R

C

C O

R

H NH2+

Strecker Aldehyde

Strecker Degradation Mechanism

-Aminocarbonyl

CH3 C

O

C

O

CH3 CH3 C

O

C

O

CH2CH3

O

OO

OCH-CH2OH

OH

Dehydroascorbic acidHO

CH3

OO

OHHO

Diacetyl 2,3-pentanedione

L-deoxyhexosone (from Amadori)

Dicarbonyl Compounds for Strecker Degradation

Compounds from Methionine by Strecker Reaction

H3C S CH2 CH2 CH COOH

NH2

CH2=CH-CHO+

+

Strecker Aldehyde

H3C-S-CH2-CH2-CHO

H3C-SH

H3C-S-CH3 H3C-S-S-S-CH3

H3C-S-S-CH3

H3C-S-S-S-S-CH3

S COOH

NH2

R CO

CO

R'

SCHO

H2O

CH3SH CH2 CHOHOH2C+

Methylmercaptan

Methionine Breakdown by Strecker Reaction

R C

O

C R '

N H2H

Enaminol

CO2

++ +

-

--

HSC O O H

N H2

R C

O

C

O

R'

HS C H2 C HO R C

O

C R'

N H2

+

H

H2S + C H3C HO + CO

R

C N H

R'EnaminolMercapto Acetaldehyde

H2S Formation from Cysteine by Strecker Reaction

CO2 +








NH3


Amino Acids




CO2 + -aminoketone



ThiazolesPyrroles

++

Retroaldol Reaction Products from Maillard Reaction

Hydroxyacetone

Hydroxyacetylaldehyde

Acetoin

Acetylaldehyde

Glyceroaldehyde

Pyruvaldehyde

Glyoxal

Diacetyl

CH2HO C CH3

OHC

O

CH

O

CH3-C

O

CH

OCH2HO CH

O

CH3CH

OH

C CH3

OHO-CH2

OH

CH-CH

O

CH3 CH

O

CH3-C

O

C-CH3

O

Pyrazines Formation

Cocoa, coffee, French fry, Roasted beef

CH2C

O

NH2

H

+CC

O

CH2OH

H

H2N - H2O

N

N CH2OH

N

N

CH2

H

OH-

N

N

CH3

CC

O

OH

HNH3 C

CO

HO

H

NH2

,-Dicarbonyl

+ CHCH2

H2N

O

N

NH

H

OH

HHO

HON

N

-3H2O

Pyrazines Formation

Oxazole Formation

Trimethyl-oxazoline in beef stew

N

O2,4,5-trimethyl oxazole

Possible mechanism for the formation of trimethyloxazoleCH 3CHO, and NH 3.from diacetyl,

H3C C

O

C

O

CH3H2O

H3C C

OH

C CH3

OH

O

H3C CH

O NH3

H3C C H

NH

+

·

H2O-

H3C C

OH

C CH3

OH

N

H3C C·

H2O-

H3C C

H3C C C CH3

O N

·

··

·N

O CH3H3C

H3C

+

+

H2O-

Mechanism for the Formation of Trimethyl-oxazoline

Thiazole Formation

(Weak nutty, sulfur) (Baked potato, beef, coffee, tea, cocoa bean)

H2S

H3C C

OH

C CH3

SH

O

NH3

H3C C H

NH

+

·

H2O-

C

OH

C CH3

SH N

H3C C·

H2O-

·

··

·

+

+

- H2O

C

O

C

O

CH3H3CH3C

CH

O

H3C

N

S CH3

H3C

H3C H3C C

H3C C C CH3

S N

Asparaginase reaction

Acrylamide minimation by AsparaginaseAcrylamide minimation by Asparaginase

Asparaginase minimize the Acrylamid concentration in baked and fried products:

• Acrylamid will substantially produced by asparagin in reaction with carbohidrates (Maillard-Reaktion)

• Asparaginase transform Asparagin in Asparatat

Acrylamide reduction by Asparaginase in different products

food acrylamide-reduction (%)

cookies 80-85%

potato-chips 80-98%

Bread-chips 84-92%

Egg cookies 64-79%

Toastbread ~ 40%

Pommes Frites 50-60%

Reduktionsmittel

Date post:	23-Oct-2015
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Maillard 2

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