2 Literature Meeting Lucie Zimmer January the 30th 2007 The Maillard ReactionThe Maillard reaction is one of the most common reaction as it occurs every time sb is cooking sth in a pan or on a bbq… It is also the reaction which occurs in the roasting of chocolate or coffee bean. And it actually also occurs during the roasting of the malt in the beer fabricationLiterature MeetingLucie ZimmerJanuary the 30th 2007
3 Brown or black pigments Characteristic odour and taste Caramel(sugars)Cream(amino compounds)BrowningBrown or black pigmentsCharacteristic odour and tasteAlteration of Nutritive propertiesBrowning of banana / reding of pastaThe Maillard reaction is the reaction which occurs when u mix sugars and proteins for instance it occurs when u mix caramel and cream and the visible consequence of this reaction is the browning which occurs with time and moderated heat. Actually one of the characteristic of the Maillard reaction is the formation of brown to black pigments which in our case colour the whole mixture…Other characteristics of the Maillard reaction is the development of a characteristic odor and taste in the food…The Maillard reaction is also responsible of the alteration of the nutritive properties of food and of the synthesis of carcinogenic and anti carcinogenic compounds. If the Maillard reaction is benefic to our papille… it has also few drawbacks like the boning of banana or a pinkish color taken by the pasta during their drying…
4 Very versatile reaction (schizophrenic?) Maillard ReactionFrom the name of the french chemist, Louis-Camille MaillardMain steps published in 1912 but still studied.Lead to the formation of many organoleptic compoundsAntioxydative and carcinogenic properties of Maillard productsThe reaction was discovered by the french chemist Louis Camille Maillard. The reaction wes icovered in 1912 but few aspects of this reaction are still unknown… the caracteristic odour of the Maillard reaction is due to the formation of organoleptic compounds like the pyrazine derivatives reported in the table…The Maillard reaction is blamed to be the responsible of the degradation of the vitamin C during cooking.On a medical point of view, the Maillard reaction is used to mesured for how long diabetic people are diabetics…But it is also the reaction responsible of the damage caused by the hyperglycemy to the tissues…It is also believed to be responsible of some aging damage forinstance the modification of the collagen.Very versatile reaction (schizophrenic?)
5 Maillard Reaction : main steps The Maillard reaction occurs in three main steps…Bristow, M.; Isaacs, N. S. J. Chem. Soc., Perkin Trans. 2, 1999,
6 Maillard Reaction : main steps Three main stepsMaillard condensation and Amadori rearrangementFormation of caracteristic compoundsMelanoidin formationThe Maillard reaction occurs in three main steps…Machiels, D.; Istasse, L. Ann. Med. Chem. 2002, 146,
7 I. Condensation de Maillard N-substitued glycosylaminesStable if from proteines or peptidesIf from aminoacids : Amadori rearrangementAldose, cetose… Every reductive sugarsAmino acids,peptides,proteinesThe Maillard condensation is the condensation the amine of an amino acid, of a peptide or of a protein onto the carbonyl function of a reductiv sugar. The condensation which occurs with the lost of a molecule of water explain why the maillard condensation occurs rather in a media not too acqueous. I mean the Maillard reaction didn’t occur when you boiled meat for instance. Not only because of the temperature which cannot exceed 100°C but mainly because the excess of water displace the equilibium in favor of the sugar and the amino compound.The N-substituted glycosamines so obtained are quiet stables when the condensation occured wih a proteines of a big peptide bt in the case of a condensation with an amino acid, the N glycosamine spontaneously rearrange by the Amadori rearrangementReaction 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 :Heyns rearrangement : (A bit slower)In thsi rearrangement, the unbonding elctron pair of the nitrogen opens the ring in forming the iminium which is in euqilibrium with the enamine/enol wich is in equilibrium with the alpha amino ketone. This tautomer is the most stable and the main recovered in solution.The same rearrangement occuring which ketose instead of aldose is called the Heyns rearrangement. The reaction has been used in few stnhess that we will look at a bit later… and overall these transformations can be used to transform a cetose in an aldose and the opposite.Application: transformation of aldose in ketose and ketose in aldose
9 II. CHARACTERISTIC COMPOUND FORMATIONThe Maillard reaction occurs in three main steps…
10 II. Characteristic compounds: formation 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 II. Characteristic compounds: formation Scission:recombination of the small moleculesLedl, F.; Scleicher, E. Angew. Chem. Int. Ed. 1990, 29,
12 II. Characteristic compounds: formation 1,2 or 2,3 enolisation followed by dehydratation:2.1 Low or neutral pH : enolisation 1,2 favoredAfter the Amadori rearrangement, two enolisations can occur: the 1,2 and the 2,3… At Low or neutral pH the 1,2 enolisation is favored. For exemple in the degradaion of glucose, after the Amadori rearrrangement, the enolisaion 1,2 occurs, followed by the lost of a molecule of water which can cleave the imine to give a 3-desoyhexlose. The 3-desoyhexlose is in equilibrium wih the di carbomyl compound. Wich after double ddehydratation and cyclisation lead to the 5-hydroxymethylfuraldehyde.Machiels, D.; Istasse, L. Ann. Med. Chem. 2002, 146,
13 II. Characteristic compounds: formation 2.2 Higher pH : 2,3 enolisationExemple: furaneol synthesis (strawberry, ananas, caramel)At higher pH, the most favored reaction after the Amadori rearrangement is the enolisation 2,3. For exemple in the synthesis of the furneol, We have first condensation of the L-Rhamnose with an amino acid… After Amadori rearrangeemntand the enolisation 2,3 occurs. After the lost of the amino acid, the hexulose undergoes the cetoenolic equilibrium and cyclisize to give this dihydrofuranone. After a dehydratation the fureanol is obtained. The fureanol is found in strawberries, ananas, and caramel…Lizzani-Cuvelier L. et al. L’Act. Chim. 2002, 04, 4-14.
14 II. Characteristic compounds: formation At « high » pH apparition of nitrogenous heteroaromatic rings.Reductones so obtained can condensate with amino ketones to give after dehydratation different kind of pyrroles:dehydratationcondensation…
15 II. Characteristic compounds: formation Strecker degradation :Reductones and dehydroreductones can undergo Strecker degradation by reacting with amino acid
16 II. Characteristic compounds: formation 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. L’Act. Chim. 2002, 04, 4-14.
17 Particular amino acids: Protein-bound tryptophane hardly reactiveOccur also in free state :No Amadori rearrangement observed if N-glycosyl derivativeIn the case of over-cooked products: formation of carcinogenic productLedl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29,
18 Particular amino acids: Occurs in large amount in cereals, particularly in malt.Lead to tastefull moleculesLedl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29,
19 Particular amino acids: Do not occur free in food stuffRelease hydrogene sulfideLow odor threshold (roasted coffee beans…)Retarding effect on the reactionLedl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29,
20 Particular amino acids: No reaction with guanido groupTrapping of carbonylated compoundsCross linking to form colored compounds.Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29,
21 Arg-pyrimidineStep which gives the taste and the color to the beer = roasting of the malt.Main parameters : time, temperature and humidity rate during the roastingGlomb et al. J. Agric. Food Chem., 2001, 49,
22 Filled circles = darker beers Arg-pyrimidineBarley, water mixtureFilled circles = darker beersEBC: European Brewery ConventionFor the same wort the darker beers have got a higher content of Arg-pyrimidineColor not only depending of Arg-pyrimidine
25 Polymerisation: Melanoidin formation Give to the meat hardness and color…No structure found to date…Mix of polymers of different molecular weightsMade by polymerisation of different heterocycles thanks to retroaldolisation products…Formation delayed by addition of waterenhanced by transition metal (Fe2+, Cu2+)
26 Maillard Reaction : in vivo… Evidence of the first products of Maillard reaction found in vivoDiabete: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 (hair’s or nails proteins)Severe complications = high degree fructolysation increased damage to eyes and kidneyAging:Maillard products accumulate in the organismeLink between aging damages and Maillard reaction… (collagen)The Maillard reaction occurs in three main steps…Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29,
27 Control of Maillard reaction to preserve food and body Kinetics:Glucose + amino acids at 2°C : two months to have light yellow colorationAdditives:Addition of sulfites : use strickly control specially because of their bad effects on asthmatic peopleStructure identified after sulfite addition :In vivo:Administration of aminoguanidine :Relatively well tolered by mammalsLowered concentration of cross-linking of collagen and deposition of cholesterol transporting lipoproteins on the arterial walls.
29 Pop corn like odorant…De Kimpe, N. G., Rochetti, M. T. J. Agric. Food Chem., 1998, 46,
30 Analogue synthesisTHT1 glucose transporter of parasite causing African sleeping sickness also accepts D-fructose.Azéma, L.; Bringaud, F.; Blonski, C.; Périé, J. Bioorg. Med. Chem. 2000, 8,
31 ApplicationsFernandez-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 ConclusionMaillard reaction lead to a huge amount of different compounds:
36 Molecular Gastronomy Nicholas Kurti Hervé This Ferran Adria, Heston Blummenthal,Pierre Gagnaire,Emile Jung,Bernard Leprince,Michel Roth,Pierre Hermé…
37 Lorsque nous cuisinons un œuf à la coque, une petite couche gris-vert apparaît parfois entre le jaune et le blanc. Il s’agit 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.Molecular GastronomyFirst target : eggs and mayonnaiseScientifical optimisation of the emulsion quality1 litre of mayonnaise from 1 yolk !Verification of adviceWhen eggs are overcooked: apparition of gray-green layer around the yolk.Iron from yolk and sulfure from white lead to FeS2 which give bad taste and color.
38 Lorsque nous cuisinons un œuf à la coque, une petite couche gris-vert apparaît parfois entre le jaune et le blanc. Il s’agit 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.Molecular GastronomyKBH4
39 Molecular Gastronomy« Pour the peas in cold water to fix the chlorophyll… »During the cooking, Mg2+ of chlorophyll are replaced by 2 H+Solution : baking soda in the cooking water….This, H. Nature Materials, 2005, 4, 5-7
40 Molecular Gastronomy« Red berries should not be cooked in tin or copper pan... »Raspberries crushed in waterRaspberries crushed with Sn2+Complexation with polyphenolsThis, H. Nature Materials, 2005, 4, 5-7.
41 Molecular Gastronomy Cheap Tips…. Whisky few drops of vaniline : ethanol + lignin of wood barrels give 4-hydroxy-3-methoxybenzaldehydeNo Mushrooms ?Use an appropriate amount of 1-octen-2-ol or benzyl trans-2-methylbutenoate
42 Molecular GastronomyMärkl, G. Angew. Chem. Int. Ed. 2003, 42,