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The Maillard Reaction Literature Meeting Lucie Zimmer January the 30 th 2007.

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Presentation on theme: "The Maillard Reaction Literature Meeting Lucie Zimmer January the 30 th 2007."— Presentation transcript:

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2 The Maillard Reaction Literature Meeting Lucie Zimmer January the 30 th 2007

3 Caramel (sugars) Cream (amino compounds) Browning Brown or black pigments Characteristic odour and taste Alteration of Nutritive properties Browning of banana / reding of pasta

4 Maillard Reaction From the name of the french chemist, Louis-Camille Maillard Main steps published in 1912 but still studied. Lead to the formation of many organoleptic compounds Antioxydative and carcinogenic properties of Maillard products Very versatile reaction (schizophrenic?)

5 Maillard Reaction : main steps Bristow, M.; Isaacs, N. S. J. Chem. Soc., Perkin Trans. 2, 1999,

6 Maillard Reaction : main steps Three main steps –Maillard condensation and Amadori rearrangement –Formation of caracteristic compounds –Melanoidin formation Machiels, D.; Istasse, L. Ann. Med. Chem. 2002, 146,

7 Aldose, cetose… Every reductive sugars Amino acids, peptides, proteines N-substitued glycosylamines Stable if from proteines or peptides If from aminoacids : Amadori rearrangement I. Condensation de Maillard Reaction easier with small sugar and amine function far from carboxylic acid moeity. (special case of lysine: rate 5-15 times higher)

8 I. Amadori and Heyns rearrangements Amadori rearrangement : Application: transformation of aldose in ketose and ketose in aldose Heyns rearrangement : ( A bit slower )

9 II. CHARACTERISTIC COMPOUND FORMATION

10 II. Characteristic compounds: formation 1.Scission: Formation of small molecules : retroaldol cleavage. Those molecule can react by aldolic condensation to give polymeres. Ledl, F.; Scleicher, E. Angew. Chem. Int. Ed. 1990, 29,

11 1.Scission: recombination of the small molecules Ledl, F.; Scleicher, E. Angew. Chem. Int. Ed. 1990, 29, II. Characteristic compounds: formation

12 2.1,2 or 2,3 enolisation followed by dehydratation: 2.1 Low or neutral pH : enolisation 1,2 favored Machiels, D.; Istasse, L. Ann. Med. Chem. 2002, 146, II. Characteristic compounds: formation

13 2.2 Higher pH : 2,3 enolisation Exemple: furaneol synthesis (strawberry, ananas, caramel) Lizzani-Cuvelier L. et al. LAct. Chim. 2002, 04, II. Characteristic compounds: formation

14 At « high » pH apparition of nitrogenous heteroaromatic rings. Reductones so obtained can condensate with amino ketones to give after dehydratation different kind of pyrroles: dehydratation condensation … II. Characteristic compounds: formation

15 3.Strecker degradation : Reductones and dehydroreductones can undergo Strecker degradation by reacting with amino acid II. Characteristic compounds: formation

16 Aminoketones can condensate and give heteroaromatics or react with another amino acid to give colored compound. Bristow, M.; Isaacs, N. S. J. Chem. Soc., Perkin Trans. 2, 1999, Lizzani-Cuvelier L. et al. LAct. Chim. 2002, 04, II. Characteristic compounds: formation

17 Particular amino acids: Protein-bound tryptophane hardly reactive Occur also in free state : Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29, No Amadori rearrangement observed if N-glycosyl derivative In the case of over-cooked products: formation of carcinogenic product

18 Particular amino acids: Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29, Occurs in large amount in cereals, particularly in malt. Lead to tastefull molecules

19 Particular amino acids: Do not occur free in food stuff Release hydrogene sulfide Low odor threshold (roasted coffee beans…) Retarding effect on the reaction Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29,

20 Particular amino acids: No reaction with guanido group Trapping of carbonylated compounds Cross linking to form colored compounds. Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29,

21 Arg-pyrimidine Step which gives the taste and the color to the beer = roasting of the malt. Main parameters : time, temperature and humidity rate during the roasting Glomb et al. J. Agric. Food Chem., 2001, 49,

22 Arg-pyrimidine EBC: European Brewery Convention Barley, water mixture Filled circles = darker beers Color not only depending of Arg-pyrimidine For the same wort the darker beers have got a higher content of Arg-pyrimidine

23 III. POLYMERISATION: MELANOIDIN FORMATION

24 III. Polymerisation: Melanoidin formation

25 Polymerisation: Melanoidin formation Give to the meat hardness and color… No structure found to date… Mix of polymers of different molecular weights Made by polymerisation of different heterocycles thanks to retroaldolisation products… Formation delayed by addition of water enhanced by transition metal (Fe 2+, Cu 2+ )

26 Maillard Reaction : in vivo… Evidence of the first products of Maillard reaction found in vivo Diabete: N-term of hemoglobin can be glycosilated = Marker of diabetic people (2-3 months) Other proteins can give shorter markers (2-3 weeks) or longer (hairs or nails proteins) Severe complications = high degree fructolysation increased damage to eyes and kidney Aging: Maillard products accumulate in the organisme Link between aging damages and Maillard reaction… (collagen) Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29,

27 Control of Maillard reaction to preserve food and body 1.Kinetics: Glucose + amino acids at 2°C : two months to have light yellow coloration 2.Additives: Addition of sulfites : use strickly control specially because of their bad effects on asthmatic people Structure identified after sulfite addition : 3.In vivo: Administration of aminoguanidine : Relatively well tolered by mammals Lowered concentration of cross-linking of collagen and deposition of cholesterol transporting lipoproteins on the arterial walls.

28 APPLICATION : HETEROCYCLE SYNTHESIS

29 Pop corn like odorant… De Kimpe, N. G., Rochetti, M. T. J. Agric. Food Chem., 1998, 46,

30 Analogue synthesis Azéma, L.; Bringaud, F.; Blonski, C.; Périé, J. Bioorg. Med. Chem. 2000, 8, THT1 glucose transporter of parasite causing African sleeping sickness also accepts D-fructose.

31 Applications Fernandez-Bolaños, J. G. et al. Tetrahedron Ass , 14, Yeagley, D. A.; Benesi, A. J., Miljkovic, M. Carbohydr. Res. 1996, 289, Horvat, S. et al. J. Chem. Soc., Perkin Trans ,

32 Application piperidinone Guzi, T. J.; Macdonald, T.L. Tetrahedron Lett. 1996, 17,

33 Application piperidinone synthesis Guzi, T. J.; Macdonald, T.L. Tetrahedron Lett. 1996, 17,

34 Application piperidinone synthesis Guzi, T. J.; Macdonald T. L. Tetrahedron Lett. 1996, 17,

35 Conclusion Maillard reaction lead to a huge amount of different compounds:

36 Molecular Gastronomy Hervé ThisNicholas Kurti Ferran Adria, Heston Blummenthal, Pierre Gagnaire, Emile Jung, Bernard Leprince, Michel Roth, Pierre Hermé…

37 Molecular Gastronomy Lorsque nous cuisinons un œuf à la coque, une petite couche gris-vert apparaît parfois entre le jaune et le blanc. Il sagit de sulfure de fer. Le soufre provient des protéines du blanc, qui sont libérées lors de la coagulation par la chaleur. Ces protéines entrent en contact avec le jaune, qui contient du fer. La réaction chimique résulte en un sulfure de fer gris ou verdâtre. La cuisson est alors manquée, parce que l'oeuf a été exposé trop longtemps à la chaleur. First target : eggs and mayonnaise Scientifical optimisation of the emulsion quality 1 litre of mayonnaise from 1 yolk ! Verification of advice When eggs are overcooked: apparition of gray-green layer around the yolk. Iron from yolk and sulfure from white lead to FeS 2 which give bad taste and color.

38 Molecular Gastronomy Lorsque nous cuisinons un œuf à la coque, une petite couche gris-vert apparaît parfois entre le jaune et le blanc. Il sagit de sulfure de fer. Le soufre provient des protéines du blanc, qui sont libérées lors de la coagulation par la chaleur. Ces protéines entrent en contact avec le jaune, qui contient du fer. La réaction chimique résulte en un sulfure de fer gris ou verdâtre. La cuisson est alors manquée, parce que l'oeuf a été exposé trop longtemps à la chaleur. KBH 4

39 Molecular Gastronomy This, H. Nature Materials, 2005, 4, 5-7 During the cooking, Mg 2+ of chlorophyll are replaced by 2 H + Solution : baking soda in the cooking water…. « Pour the peas in cold water to fix the chlorophyll… »

40 Molecular Gastronomy This, H. Nature Materials, 2005, 4, 5-7. Raspberries crushed with Sn 2+ Complexation with polyphenols Raspberries crushed in water « Red berries should not be cooked in tin or copper pan... »

41 Molecular Gastronomy Cheap Tips…. Whisky few drops of vaniline : ethanol + lignin of wood barrels give 4-hydroxy-3-methoxybenzaldehyde No Mushrooms ? Use an appropriate amount of 1-octen-2-ol or benzyl trans-2-methylbutenoate

42 Molecular Gastronomy Märkl, G. Angew. Chem. Int. Ed. 2003, 42,


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