Microsoft Word - fullpdf06012024 Georgian Scientists/ქართველი მეცნიერები ტ. 6 N 1, 2024 112 Georgian Scientists ქართველი მეცნიერები Vol. 6 Issue 1, 2024 https://doi.org/10.52340/gs.2024.06.01.14 Formation of taste and aroma compounds by Maillard reaction during processing of food products Nona Bolkvadze 1, Sophio Gvidani 2, Rusudan Uridia 3, Nana Tserodze 3, Nino Kavtaradze 3, Leila Tatiashvili 3, Nino Karkashadze 3 1 Georgian Technical University 2 Iv. Javakhishvili Tbilisi State University, Al. Natishvili Morphology Institute 3 Iv. Javakhishvili Tbilisi State University, P. Melikishvili Institute of Physical and Organic Chemistry Abstract. The Maillard reaction plays an especially important role in the thermal processing of food products. During the heat treatment of vegetable and animal products, glucose and fructose, formed as a result of sucrose hydrolysis, are mainly involved in the sugar-amine reaction as a carbohydrate component, while free amino acids and proteins are used as an amino component. The compounds formed during the Maillard reaction determine the aroma and taste of the thermally treated product [1]. Recently, it was found that the Maillard reaction occurs also in the body [2]. Excess glucose in the body is assumed to bind to proteins through the Maillard reaction, leading to early aging, atherosclerosis, diabetes, and other diseases [3]. The smell and taste of products are due to the compounds resulting from the Maillard reaction in food processing. In products of plant, animal, or microbial origin, all conditions are present (the content of sugars, amino acids, proteins, water, acidic, neutral, or basic medium) promoting the processes involved in the Maillard reaction. and different types of heat treatment as baking, roasting, boiling, and drying cause these processes at different intensities. Key Words: Maillard reaction, amino acid, aromatic compounds, flavor compounds Georgian Scientists/ქართველი მეცნიერები ტ. 6 N 1, 2024 113 Introduction The Maillard reaction plays an especially important role in the thermal processing of food products. During the heat treatment of vegetable and animal products, glucose and fructose, formed as a result of sucrose hydrolysis, are mainly involved in the sugar-amine reaction as a carbohydrate component, while free amino acids and proteins are used as an amino component. The compounds formed during the Maillard reaction determine the aroma and taste of the thermally treated product [1]. Recently, it was found that the Maillard reaction occurs also in the body [2]. Excess glucose in the body is assumed to bind to proteins through the Maillard reaction, leading to early aging, atherosclerosis, diabetes, and other diseases [3]. The smell and taste of products are due to the compounds resulting from the Maillard reaction in food processing (Scheme 1). In products of plant, animal, or microbial origin, all conditions are present (the content of sugars, amino acids, proteins, water, acidic, neutral, or basic medium) promoting the processes involved in the Maillard reaction. and different types of heat treatment as baking, roasting, boiling, and drying cause these processes at different intensities. During the processing of food products, aromatic compounds are mainly formed in the second stage of the Maillard reaction [4]. First of all, the oxidative degradation of α-amino acids by dicarbonyl compounds is particularly important. During this process formed aldehydes contain one carbon atom less than the original amino acid. Such an oxidation is named Strecker degradation. A necessary condition for this reaction is that he amino group must be in the α-position, and the dicarbonyl compound must contain the following groups: - C - C - OO - C - (CH = CH)n - C - OO or The reaction is expressed by the equation: R-CO-CO-R' + R"-CH(NH2)-COOH R"-CHO + CO2 + R-CH(NH2)-CO-R' If the hydrogen atom at the α-carbon of the amino acid is substituted, than a ketone is obtained. Georgian Scientists/ქართველი მეცნიერები ტ. 6 N 1, 2024 114 Reducing sugars + α-Amino acids N Glycosylamines or N Fructosylamine 1-amino-1-deoxy-2-ketose (called Amadori rearrangement product) or 2-amino-2-deoxy – 1-aldose (Heyns rearrangement product) H2S Reductones and Dehydroreductones NH3 Amino Strecker acids degradation Retro aldol condensation Furanes Hydroxyacetone Pyruvaldehyde Aldehydes Thiophene Hydroxyacetaldehyde Glyoxal α-amino ketones Pyrroles Acetone Glyceraldehyde (Methional , NH3 H2S) Acetaldehyde Heterocyclization Pyrazines Thiazoles Pyridine Pyrroles Oxazoles Scheme 1. Formation of aromatic and flavor compounds as a result of Maillard reaction Table 1 shows the aroma obtained by heating some mixtures containing α-amino acid and glucose in an equimolar ratio (1:1 [4]. The author of this research notes that the odor of the reaction mixture is quite different from that of the corresponding pure aldehyde. The same mixture produces different aromas at different temperatures, indicating that the aldehydes produced by Strecker degradation react with other compounds in the melanoid medium to form new aroma compounds. Georgian Scientists/ქართველი მეცნიერები ტ. 6 N 1, 2024 115 Such products of sugar-amino acid reaction are 2-furaldehyde, which has the flavor of baked bread and maltol, having a mild, caramel-like flavor. Initially, maltol was isolated from autoclaving products of glycine-maltose and glycine-lactose aqueous solutions by Patton with a yield of 0.2% [5]. Further investigations have revealed that in the Maillard reaction maltol is always formed from 4-oxygen- substituted glucose, such as maltose, lactose, cellobiose, malto-oligosaccharides [3]. Maltol The Maillard reaction of a mixture of glucose and α-alanine yielded the inner salt of N-(1- carboxyethyl)-6-(hydroxymethyl)-pyridinium-3-ol. It has no taste but is a mild enhancer of sweet taste, and it is a melanoidin-derivative non-volatile sweetness enhancer [5]. During the Strecker degradation, an especially important role in the formation of aromatic components together with aldehydes play such compounds as 3-deoxyhexozones, which contain α-dicarbon grouping on C1 and C2 carbon atoms, and methyl-α-dicarbon intermediate products, having such grouping on C2 and C3 carbon atoms. 3-deoxyhexozones, Both types of α-dicarboxylic intermediates can produce flavor compounds, for example, furaldehydes from 3-deoxyhexozones, and acetaldehyde, pyruvaldehyde, diacetyl, and acetic acid by cleavage of methyl-α-dicarboxylic intermediates and their dehydration products. It should be noted that these products are produced from sugars also without amino compounds. In particular, as a result of 1,2-enolization of sugars in the process of caramelization. At a high temperature, in a strong acid or strong base medium, the hydroxyl group located at the C3 and C1 carbon atoms are eliminated. Condensation with amino compounds, however, allows such enolisation and elimination to occur in a neutral region and at lower temperatures [6]. Important aroma-active compounds furanoses are formed from 1-deoxy-ozone: Pentoses further react with amines to form orange dyes, which determine the color of the food product: Georgian Scientists/ქართველი მეცნიერები ტ. 6 N 1, 2024 116 Compounds formed from 3-deoxy-ozones contain fragments of pyrrole, pyridine, and formylpyrrole. As a result of the condensation of two amino ketones, various pyrazine derivatives can be formed, which are also aroma-active compounds: Table 1. Aroma obtained by heating some mixtures containing α-amino acid and glucose (1:1) [7] α-amino acid R-CH(NH2)COOH R= Aldehyde R-CHO Flavor 100 0C 1800C Glycine H- Formaldehyde Caramel Burnt sugar α - Alanine CH3- Acetaldehyde Caramel Burnt sugar α-Aminobutyric acid CH3- CH2- Propionaldehyde Caramel Burnt sugar Valine (CH3)2- CH- 2-methylpropanal Rye bread Intense chocolate Leucine (CH3)2- CH- CH2- Isovaleraldehyde Fruit Burnt cheese Isoleucine CH3- CH2- CH- (CH3)- 2-methylbutanal Mold, fruit Burnt cheese Serine HO- CH2- Glycoaldehyde Maple syrup Threonine CH3- CHOH- Lactaldehyde Chocolate Burning smell Methionine CH3- S- CH2- CH2- Methional Potatoes Potatoes Phenylglycine C6H5- Benzaldehyde Bitter almonds Phenylalanine C6H5 - CH2- α - Tolualdehyde Smell of violet, rose smell of Violet, rose, lilac Tyrosine HO- C6H4 - CH2- Caramel Proline of burnt protein pleasant, of baked Georgian Scientists/ქართველი მეცნიერები ტ. 6 N 1, 2024 117 Hydroxyproline Potatoes Histidine Does not have Cornpone Arginine H2N-C=NH-NH-(CH 2)2- Weak, of butter Lysine-HCl H2N-(CH2)4- Does not have Similar to bread Aspartic acid HOOC- CH 2 - Ice-caramel Caramel Glutamic acid HOOC- CH2 - CH 2 - Caramel Burnt sugar Glutamine H 2N-CO- CH2 -CH 2 - Pleasant, of chocolate Iris Cysteine-HCl HS- CH 2 - Sulfide, meat Cystine -CH2 -S-S - CH 2 - Sulfide, burned skin According to the data many representatives of aroma and taste compounds, including heterocyclic compounds, are formed as a result of the thermal degradation of melanoidin products at 1000C and higher temperatures. For example, during heat treatment of melanoidin produced on the base of glucose-glycine (120, 150, and 180 0C), pyrazines made up 54-79% of the total amount of volatile compounds. Pyrroles, ketones, furans, oxazoles, and pyridines were also identified among the volatile products. The reaction pH and pressure significantly affect the direction and intensity of the thermal degradation process [8-10]. Through the thermal degradation of this type of melanoidin's (100-3000C), the maximum formation of furans, pyrroles, pyrazines, and carbonyl compounds was observed at 200- 2200C, and of pyridines and oxazoles at higher temperatures [11]. REFERENCES: 1. Belitz H.D., Grosh W. Food Chemistry. Berleih, Heidelberg, New York. Springer-Verlag. 199, 263- 318. 2. Biemel K.M., Friedl D.A., Lederer M.O. Identification and Quantification of Major Maillard Cross – links in Human Serum Albumuh and Lens Protein.Evidence fon Ghucosepans as the Dominant Compound. J. Bio. Chem., 2002, 277, 24907-24915. Georgian Scientists/ქართველი მეცნიერები ტ. 6 N 1, 2024 118 3. Van Boekel M.A. The Role of Glycation in Aging and Diabetes Mellitus. Mol. Biol. Rep., 1991. 15. 57-64. 4. Hodge J.E. Fisher B.E. Nelson E.C. Dicarbonyls, reductones, and heterocyclycs produced by the reactions of reducing sugars with secondary amine salts. Am. Soc. Brew. Chem. Proc., 1963, p. 84-92. 5. Patton S. the formation of maltol in certain carbohydrate-glycine systems. J. Biol. Chem., 1950, v. 184, p. 131-134 6. Hofmann T. Quantitative studies on the role of browning precursors in the Maillard reaction of pentoses and hexoses with L-alanine. Europ. Food Res. Technol., 1999, v 209, p. 113-121 7. Ames J.M. Guy R.C. kipping G.J. Effect of pH, temperature, and moisture on the formation pf volatile compounds in glycine/glucose model systems. J. Agric. Food. Chem., 2001, v. 49, p. 4315-4323. 8. Hodge J.E. Chemistry of browning reactions in model systems. J. Agric. Food Chem., 1953, v. 1, p. 928-943 9. Moreno F.J., Molina E., Olano A., Lopez-fandino R.J. High-pressure effects on Millard reaction between glucose and lysine. J. Agric. Food Chem., 2003, v. 51, p. 394-400. 10. Tehrani K.A., Kersiene M., Adams A., Venskutonis R., De Kimpe N. Thermal degradation studies of glucose/glycine melanoidins. J. Agric. Food Chem., 2002, v. 50, p. 4062-4068. 11. Hodge J.E. Nonenzymatic browning reactions. In the Chemistry and Physiology of Flavors (Schultz H.W., Day E.A., Libey L.M. Eds) Westport, Connecticunt: A VI Publ. Company, Inc., 1967, p. 465-491. საკვები პროდუქტების გადამუშავების დროს საგემოვნო და სურნელოვანი ნაერთების წარმოქმნა მაილარდის რეაქციით ნონა ბოლქვაძე1 , სოფიო გვიდანი 2, რუსუდან ურიდია 3, ნანა წეროძე 3, ნინო ქავთარაძე 3, ლეილა ტატიაშვილი 3, ნინო ქარქაშაძე 3 1 საქართველოს ტექნიკური უნივერსიტეტი 2 ივ. ჯავახიშვილის სახელობის სახელმწიფო უნივერსიტეტის ალ. ნათიშვილის მორფოლოგიის ინსტიტუტი 3 ივ. ჯავახიშვილის სახელობის სახელმწიფო უნივერსიტეტის პ. მელიქიშვილის ფიზიკური და ორგანული ქიმიის ინსტიტუტი მაილარდის რეაქცია განსაკუთრებით მნიშვნელოვან როლს ასრულებს კვების პროდუქტების თერმოდამუშავების პროცესში. მცენარეული და ცხოველური პროდუქტების თერმოდამუშავებისას შაქარ-ამინურ რეაქციაში ნახშირწყლოვანი კომპონენტის სახით ძირითადად თავისუფალი ან საქაროზას ჰიდროლიზის შედეგად წარმოქმნილი გლუკოზა და ფრუქტოზა, ხოლო ამინური კომპონენტის სახით თავისუფალი ამინომჟავები და ცილები მონაწილეობს. მაილარდის რეაქციის პროცესში წარმოქმნილი ნაერთები ფაქტობრივად განსაზღვრავს თერმულად დამუშავებული პროდუქტის არომატსა და გემოს [1] Georgian Scientists/ქართველი მეცნიერები ტ. 6 N 1, 2024 119 ბოლო დროს დადგინდა, რომ მაილარდის რეაქცია ორგანიზმშიც მიმდინარეობს [2] როგორც ვარაუდობენ ორგანიზმში ჭარბი გლუკოზა მაილარდის რეაქციის საშუალებით უერთდება ცილებს, რაც იწვევს ადრეულ სიბერეს, ათეროსკლეროზს, დიაბეტსა დასხვა დაავადებებს [3] საკვები პროდუქტების გადამუშავების პროცესში მაილარდის რეაქციის შედეგად წარმოქმნილი ნაერთებითაა განპირობებული პროდუქტების სურნელი და გემო. მცენარეული, ცხოველური ან მიკრობული წარმოშობის პროდუქტებში ყველა პირობა არსებობს (შაქრების, ამინომჟავების, ცილების, წყლის შემცველობა, მჟავე, ნეიტრალური ან ფუძე არე) იმ პროცესების წარმათვისათვის, რომლებსაც მაილარდის რეაქცია მოიცავს, ხოლო თერმოდამუშავების ისეთი სახეები, როგორიცაა ცხობა, შეწვა, ხარშვა, შრობა სხვადასხვა ინტენსივობით წარმართავს ამ პროცესებს. საკვანძო სიტყვები: მაილარდის რეაქცია, ამინომჟავები, სურნელოვანი ნაერთები, საგემოვნო ნაერთები