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International Journal of Advanced Science and Technology Vol. 29, No. 6, (2020), pp. 5078 - 5086 Characteristics, Mechanism, and Applications of The Caramelization and Maillard Reaction Product – A Review Edy Subroto1*, Resky Iman Firtian2 Department of Food Industrial Technology, Faculty of Agro-Industrial Technology, Universitas Padjadjaran, Jl.Raya Bandung-Sumedang Km. 21, Jatinangor, Sumedang 40600, Indonesia. [email protected], [email protected] Abstract Browning reaction is a reaction that causes brown on various food products. Browning reaction is divided into two, namely enzymatic and non-enzymatic. Non-enzymatic browning includes the Maillard reaction and caramelization. This review discusses the Maillard and caramelization reaction, which provides for its characteristics, mechanisms, and applications in various food products. The Maillard reaction is a browning reaction that involves reducing sugars and amine groups, which can be supported at high temperatures to produce a final product in the form of a brown polymer. Maillard reactions can be used in various food processing. Another non-enzymatic browning is caramelization. This reaction does not involve amino compounds but requires high temperatures and produces the final product in the form of a brown polymer. Caramelization reactions usually occur in ingredients or food products that have high carbohydrates or sugar, including candy, sugar syrup, bread, biscuits, nutrition bars, and muffins. Therefore the Maillard and caramelization reaction has the potential to continue to be developed in improving the quality of various food products. Keywords: Browning, caramelization, Maillard reaction, sugar, amine group 1. Introduction Some food products such as bread, chocolate candy, biscuits, and coffee are some of the food products that are brown that are favored by consumers. The formation of the brown color is the result of the browning reaction during the processing. Browning reactions are divided into two, namely, enzymatic and non-enzymatic reactions [1]. Enzymatic browning is usually triggered by polyphenol oxidase. Whereas non-enzymatic browning generally occurs through the Maillard and caramelization reactions. These reactions have been widely studied and utilized in various fields of food processing, medical, and pharmaceutical because they have beneficial quality aspects and nutritional aspects [2]–[5]. Maillard reaction is a reaction that occurs between an amine group of an amino acid or protein with a reducing sugar that can be triggered in the presence of high temperatures. The result of the Maillard reaction is a pigment complex called Melanoidin [5], [6]. Unlike Maillard, caramelization is a reaction to sugar degradation due to heat or high temperatures. Maillard reactions generally occur at relatively basic pH (9-10.5). In contrast, at low pH, the amine group is partially protonated so that only a few amino acids are available for the Maillard reaction. Maillard reaction can be conducted by adding invert sugar such as glucose and certain amino acids to increase the desired Maillard reaction [7]–[9]. There are some similarities and differences between the browning reaction by the Maillard reaction and caramelization. Maillard and caramelization reactions both do 5078 ISSN: 2005-4238 IJAST Copyright ⓒ 2020 SERSC International Journal of Advanced Science and Technology Vol. 29, No. 6, (2020), pp. 5078 - 5086 not require oxygen and can occur at both acidic and basic pH [10]. The differences are the Maillard reaction requires an amine group while caramelization does not. Maillard reactions can occur at medium and high aw temperatures, while caramelization requires high temperatures and low aw [11]. Some production processes that utilize Maillard and caramelization reactions include baking bread, coffee roasting, chocolate product processing, and others. This review aims to discuss browning by the Maillard reaction and caramelization, which provides for characteristics, mechanisms, and applications, especially in the food products. 2. Maillard's reaction Maillard's reaction was discovered in 1912 and was named by a French scientist named Louis Camille Maillard (1878-1936) [5], [11]. The reaction is usually interpreted as a non-enzymatic browning reaction. The reaction mainly occurs when food is processed or cooked at high temperatures. The reaction occurs when free amine groups of amino acids or proteins react with reducing sugars, which produce a brown color and the appearance of different flavors. Therefore Maillard reactions are often used in the food industry to add value, especially to color, taste, and flavor [12]. Several studies have shown that products resulting from Maillard reactions (MRPs) may be able to trigger pathological processes such as degenerative diseases, cataracts, diabetes, atherosclerosis, and chronic kidney failure. There are some opinions that humans who consume processed meat, pizza, or snacks that experience browning, can trigger insulin resistance and metabolic syndrome [13]. On the other hand, these Maillard reaction products (MRPs) can contribute to the important sensory attributes of thermally processed food products, especially in taste, flavor, appearance, and texture [14]. Maillard reaction products (MRPs) that are formed during food processing can also provide benefits for health or prevent disease because they have antioxidant activity [8], [15]. One of the benefits of Maillard's reaction to health is in the daily diet that has been highlighted by many researchers. Therefore it is very important to characterize and determine these products to achieve the best balance between potential risks and benefits to obtain foods that can have a good effect [16]. In the initial stages of the reaction, an increase in the functional properties of the protein generally changes, then after that, the antioxidant compounds, flavor, and brown color are formed. The intensity of the brown color of the Maillard reaction shows the higher antioxidant activity [8], [15]. However, the loss of lysine and the decrease in digestibility of protein may occur together with the reduction of some anti-nutritive, toxic, or mutagenic compounds [17]. 2.1 Maillard reaction mechanism Maillard reactions can occur between reducing sugars or other carbohydrates that have a reducing group with a primary amine group of a protein or amino acid [5], [6]. Amine groups are usually derived from free amino acids, proteins, and peptides resulting from partial hydrolysis of proteins, which are partially bioactive peptides [18], [19]. The reactions produce a brown product, which is often desired but sometimes a sign of a deterioration in the quality of food. Maillard's reaction takes place through several stages, starting with the presence of an aldose sugar or ketose sugar, which can react back and forth with amino acids or with an amino group from protein to produce Schiff base. These changes occur according to the Amadori reaction so that it becomes amino ketose compounds. The products produced by the 5079 ISSN: 2005-4238 IJAST Copyright ⓒ 2020 SERSC International Journal of Advanced Science and Technology Vol. 29, No. 6, (2020), pp. 5078 - 5086 Amadori reaction then dehydrate to form furfuraldehyde derivatives; for example, hydroxy methyl furfural (HMF) will be obtained from hexose. The dehydration process then produces a product between methyl α-dicarbonyl followed by decomposition to produce reductors and α-dicarboxyl, such as methylglyoxal, acetol, and diacetyl. These active aldehydes are then polymerized without including amino groups (called aldol condensation) or with amino groups to form brown compounds called Melanoidin. At the end of the reaction, a melanoidin brown pigment is formed, which has a large molecular weight [5], [6]. The Maillard reaction is strongly affected by the availability of aldehyde/ketone and amino groups. Besides, other factors that can affect the Maillard reaction are pH, temperature, water content, and sugar type [6], [20]. The occurrence of the Maillard reaction process is always related to temperature. This reaction will take place quickly when at a high temperature of ±100 ºC, but will not occur when at temperatures above 150 ºC. Maillard reactions take place optimum if the water content of the material or product about 10-15%, but the reaction will take place slowly if the value of the water content is too high or lower than the specified amount. In food ingredients or products that have a low pH, the protonated amino groups are more numerous, so they are not available for the Maillard reaction to take place. Generally, smaller sugar molecules can react faster than sugars that have larger molecules. In this case, this stereochemical configuration also affects the Maillard reaction; for example, in fellow hexose molecules, galactose is more reactive than others [10], [21]. 2.2 Maillard reaction applications Maillard reaction can occur and be used in various food processing, such as coffee processing, meat processing, pasta processing, milk processing, and others. Coffee is one of the important products for the lives. Coffee has become the second most enjoyed beverage after mineral water [22]. The flavor of the desired coffee drink increases during the roasting process of the coffee beans. During the roasting process, the temperature in the coffee reaches more than 180 °C, where there will be a Maillard reaction, pyrolysis of organic compounds, and caramelization of carbohydrates. At the time of roasting, the