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 Maillard reaction will produce Melanoidin. Melanoidin is formed by the polymerization of furan and pyrrole during the roasting process where the Maillard reaction occurs and is bound by an adverse polycondensation reaction. The coffee beans lose carbohydrate, protein, and fat compounds during the roasting process, but the amount of caffeine in coffee is relatively stable during roasting. Maillard reaction products (MRPs) in roasted coffee have been confirmed to contribute to the antioxidant activity of coffee that is roasted through the mechanism of donating one electron or transferring hydrogen atoms [23]. MRPs, niacin, caffeine, and other compounds contained in coffee beans can also protect teeth from damage caused by Streptococcus mutants, which are considered as the main causes for tooth decay in humans [24].

Maillard reaction can occur and be used in meat processing. Maillard reaction products (MRPs) such as heterocyclic amine (HCA) increase with the high temperature of cooking. It also appears and is more apparent in meat processing. Meat is usually cooked at high temperatures by burning, boiling, frying, and stoving, but the results of various processing can potentially trigger cancer in humans [25]. However, some studies have not been able to find a correlation between HCA and cancer risk [26]. Several studies have proven that cooking processes such as ordinary frying and high-temperature frying can trigger the high formation of (HCA). Conversely, (HCA) can produce different tastes and flavors in 5080 ISSN: 2005-4238 IJAST Copyright ⓒ 2020 SERSC International Journal of Advanced Science and Technology Vol. 29, No. 6, (2020), pp. 5078 - 5086 food. The heterocyclic compounds such as oxazole, pyrazine, and thiazole are the main compounds that can form flavors in roasting products, which are also commonly found in smoke [27]. During the high heat treatment roasting process, pyrazine will increase. Therefore, alkyl pyrazine will be produced from Strecker's degradation through condensation of intermediate products from the Maillard reaction pathway, namely two alpha amino ketone molecules [28]. Liao et al. [29] found that the appropriate methods for processing meat in the formation of MRP are frying and boiling using a microwave. Other studies reported that that roasting using charcoal has a high HCA value compared to meat fried in a frying pan. They found that roasting reduced HCA significantly [30]. In other studies, meat steaks and hamburgers were processed using a frying pan and oven. The results showed that roasting meat has little HCAs compared to other methods [31]. At this time, people prefer to consume fast food because they do not have much time to pay attention to the value of HCAs in some fast food. In the past, they reported that chicken skin has a higher HCA than meat. In other foods that have been assessed, HCA values are found in the following order: chicken, pepperoni, and deli meat products. The study found that commercially processed meats and meats in restaurants contain little HCA [32].

Other foods that can involve the Maillard reaction are pasta processing. Pasta is one food that is suitable for daily diet, so the level of consumption is increasing in several countries of the world. Pasta has several varieties and forms, (± 310) different types have been recorded. Different ways of processing pasta such as drying, forming/molding, kneading, and mixing can have an impact on the quality of the pasta. Drying is the most important stage for product quality. In traditional drying, low temperature (29-40 °C) is required but takes 24-60 hours. Therefore, high-temperature short-time (HTST) processing methods are widely used to shorten the time and increase production. Pasta processing using high temperatures has several advantages for cost, productivity, color intensity, and nutritional value [33], [34]. In the process of the pasta, drying will form several MRPs. Hellwig et al. [35] reported that in commercial pasta products, MRP N-ε-maltulosyllysine contributed the most to pasta products due to the drying process. In addition, several other MRPS such as HMF, maltosine, pyrraline, and glucosyl isomaltol are also formed during paste drying. The application of high temperature drying to the pasta can increase density and reduce adhesiveness. Besides, the benefits of high-temperature treatment lead to the formation of MRP, which can ultimately affect the color, flavor, nutritional value, and functional properties. Furosine can be widely used as an assessment of the quality of pasta. The study found that processing pasta at high temperatures can reduce the total value of carotenoids [36]. Besides furosine, maltulose can also be used as a benchmark for pasta quality.

Maillard reactions also often occur in milk processing. Milk has protein content in the form of casein and whey and has a sugar content, especially lactose which is quite high. High protein and sugar content in milk can trigger the formation of MRPs, especially if experiencing high-temperature treatment or storage. Aktağ et al. [37] reported that more hydrolyzed lactose and the addition or fortification of protein in UHT milk could increase the potential for a Maillard reaction to produce MRPs. MRPs also increase if the temperature is higher and the amount of monosaccharides is higher. However, MRPs from the Maillard reaction in milk protein has advantages, especially in increasing antioxidant activity [38]. Several methods have been tried to determine MRP levels during milk processing [39]. Lactose in milk inhibits the amino group of lysine to form an Amadori compound called Lactulosyllysine, which can change the bioavailability of proteins. The formation of MRP affects the believability of proteins and minerals. So processing

5081 ISSN: 2005-4238 IJAST Copyright ⓒ 2020 SERSC International Journal of Advanced Science and Technology Vol. 29, No. 6, (2020), pp. 5078 - 5086 milk using high temperatures requires more attention because milk is a source of nutrition that is needed, especially by children and toddlers.

3. Caramelization reaction

Caramelization is a non-enzymatic browning in sugars that require high temperatures, without involving amino compounds. This reaction is a degradation of sugar, which produces the final product in the form of a brown polymer. The caramelization process involves three reaction stages, namely the 1,2-enolization stage, the dehydration or fission stage, and the pigment formation stage [40].

Caramel pigments have several types. Each type has specific properties that are suitable for the product and can eliminate undesirable properties, such as fog, flocculation, and suspension. Caramel pigments are dark brown to black, have the flavor like burning sugar and a rather bitter taste. Caramel pigments can dissolve in water and contain colloidal aggregates which affect the coloring properties and characteristics of acids, electrolytes, and tannins [41]. Caramel can also affect consumer perceptions of the texture, especially the stickiness of food, so that it can affect the quality of food products [42].

Some researchers describe the chemical characteristics and specifications of the caramel color class. There are four different types of caramel colors for the food and beverage products, namely caramel I, caramel II, caramel III, and caramel IV. The standard property of caramel types into four classes has been set by the International Technical Caramel Association (ITCA) and the European Technical Caramel Association (EUTECA), namely class I-E150a, class II-E150b, class III-E150c, and class IV-E150d with intensity colors about 0.01-0.012, 0.06-0.1, 0.08-0.036, and 0.1-0.6, respectively [41], [43].

3.1 Caramelization reaction mechanism

The caramelization reaction mechanism involves several steps, namely starting with the process of sugar enolization such as glucose and fructose, producing 1,2- enol compounds through the heating process. If under acidic conditions, this reaction can occur more quickly. The next step 1,2-enol can experience two possibilities, namely, dehydration reaction or fission. In the dehydration reaction, the 5-hydroxymethyl-2-furaldehyde compound, which is one of the brown pigment precursors, will be produced. Dehydration reaction will occur on heating the sugar solution under acidic conditions and reaching a maximum at a pH below 3; this reaction can be called an acid degradation reaction. In the fission stage, 1,2-enol breakdown occurs to produce reducton compounds such as enadiol and pyruvaldehyde, which are also brown pigment precursors. The fission process occurs under alkaline conditions on the packing of sugar, but can also occur under weakly acidic conditions. The fission process will increase rapidly when the pH of the system increases. This process is also called a base degradation reaction, and the last step is the formation of polymerization and condensation for the formation of brown pigments [41], [44].

3.2 Application of caramelization reaction in food products

Sucrose or sugar solution, which is heated until all the water content in it is evaporated, then the liquid in it is no longer composed of water. Still, sucrose or melted sugar then goes to the caramelization reaction. The caramelization of sucrose or sugar occurs if the sugar that has been melted continues to be heated until it 5082 ISSN: 2005-4238 IJAST Copyright ⓒ 2020 SERSC International Journal of Advanced Science and Technology Vol. 29, No. 6, (2020), pp. 5078 - 5086 exceeds its melting point, which is at a temperature of about 170 ºC [45]. Generally, the reactions that occur in caramelization begin by the breakdown of the sucrose molecule into a molecule of glucose and fructosan (fructose, which loses one water molecule). High temperatures can remove water molecules from each sugar molecule so that it produces glucosan (a molecule that is analogous to fructosan). The process of hydrolysis and dehydration is then followed by the polymerization process, which produces a brownish color [46].

Brownish color pigment resulting from the caramelization of sugar has been widely used for various food industries. In the manufacture of bread, many have used caramel color to improve the color and appearance of the bread product. Caramel suitability in water and dough systems is very suitable for the application of these bakery products. Caramel color class III or IV is most often used in bakery products. Caramel also is used to guard or prevent variations in color changes during processing [41].

Caramel has a broad spectrum of colors from yellow, brown to black making it a versatile color used to improve the appearance of roasting products. In making bread, caramel can be used both in liquid and powder form, depending on the processing techniques and available equipment. Some bread makers choose the type of powder because it is not easily damaged and is durable, practical, or easy to use, and is very suitable for dry mixing [47]. Caramel powder has the advantage of being able to mix when mixing ingredients. Caramel plays a very important role in the muffin, cake, and bread products because it can improve the appearance of the final product. Caramel powder has a role in replacing synthetic dyes for a variety of chocolate cakes, puddings, and other desserts. Caramel coloring can be an alternative to cocoa powder, which is widely used in the food industry. Caramel color is usually darker than most cocoa powder, which is often used in the baking process. Therefore, the use of caramel coloring can save to reduce the need for cocoa powder used [41].

Caramel is not easily damaged due to high temperature or high-pressure treatment of an extrusion process. Caramel is not owned by natural pigment. Various cereal products have also been using caramel coloring. Likewise, a variety of snacks have used caramel powder coloring at the same time, aiming to equalize the color of the spice mixture. Various processed products can use caramel in liquid or powder form [48]. The recommended use of caramel coloring has been adjusted according to the type of product and the kind of caramel used. Some of them are: bread products can use caramel class III (liquid) (CI 110) about 1% or caramel class III (powder) (CI 190) as much as 0.5%. As for cereal products, biscuits, and muffins can be used caramel class III (powder), about 2%, 0.5-5%, and 1-3%, respectively. Whereas in nutrition bar products, caramel class I (liquid) (CI 35) is used as much as 1-2% [41].

Caramel can also be applied to various beverage products and dairy products. Ramírez-Sucre and Velez-Ruiz [49] applied caramel to yogurt to improve the color and flavor. The results of the study indicate that the addition of caramel increased panelists' acceptance for the attributes of consistency, flavor, color, and overall acceptability of yogurt. The development of fizzy drinks and beverages with synthetic sweeteners such as aspartame acid and caramel coloring has been used and patented by Zablocki and Vevang [50]. They focus on the production of beverages that use positively charged caramel coloring as a substitute for the negatively charged caramel found in conventional drinks [51].

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4. Conclusion

Non-enzymatic browning reactions include the Maillard and caramelization reactions. Maillard reaction is a browning reaction in which amino acid compounds react with reducing sugars in food. Maillard reactions can occur without heating but will be faster at high temperatures. This reaction can occur and be used in various food processing such as meat, coffee, milk, and pasta. Whereas the caramelization reaction is the degradation of sugar at high temperatures, which results in the final product being a polymer without nitrogen, which is brown. Caramelization usually occurs in ingredients or food products that have high carbohydrates or sugar. The caramel produced can be used as a coloring agent in various food products, such as bread, muffins, cakes, biscuits, and various beverages.

Acknowledgments The authors say thank you profusely to the Rector of Universitas Padjadjaran, and The Ministry of Education and Culture of the Republic of Indonesia for the support provided.

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