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Browning is the process of food turning
brown Brown is a color. It can be considered a composite color, but it is mainly a darker shade of orange. In the CMYK color model used in printing or painting, brown is usually made by combining the colors orange and black. In the RGB color model ...
due to the
chemical reactions A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking ...
that take place within. The process of browning is one of the chemical reactions that take place in food chemistry and represents an interesting research topic regarding health,
nutrition Nutrition is the biochemical and physiological process by which an organism uses food to support its life. It provides organisms with nutrients, which can be metabolized to create energy and chemical structures. Failure to obtain sufficient ...
, and
food technology Food technology is a branch of food science that deals with the production, preservation, quality control and research and development of the food products. Early scientific research into food technology concentrated on food preservation. ...
. Though there are many different ways food chemically changes over time, browning in particular falls into two main categories: enzymatic versus non-enzymatic browning processes. Browning has many important implications on the
food industry The food industry is a complex, global network of diverse businesses that supplies most of the food consumed by the world's population. The food industry today has become highly diversified, with manufacturing ranging from small, traditional, ...
relating to nutrition, technology, and economic cost. Researchers are especially interested in studying the control (inhibition) of browning and the different methods that can be employed to maximize this inhibition and ultimately prolong the shelf life of food.


Enzymatic browning

Enzymatic browning is one of the most important reactions that takes place in most fruits and vegetables as well as in seafood. These processes affect the taste, color, and value of such foods. Generally, it is a chemical reaction involving
polyphenol oxidase Polyphenol oxidase (PPO; also polyphenol oxidase i, chloroplastic), an enzyme involved in fruit browning, is a tetramer that contains four atoms of copper per molecule. PPO may accept monophenols and/or ''o''-diphenols as substrates. The ...
(PPO), catechol oxidase, and other
enzyme Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products ...
s that create
melanin Melanin (; from el, μέλας, melas, black, dark) is a broad term for a group of natural pigments found in most organisms. Eumelanin is produced through a multistage chemical process known as melanogenesis, where the oxidation of the amino ...
s and benzoquinone from
natural phenol In biochemistry, naturally occurring phenols are natural products containing at least one phenol functional group. Phenolic compounds are produced by plants and microorganisms. Organisms sometimes synthesize phenolic compounds in response to ecol ...
s. Enzymatic browning (also called oxidation of foods) requires exposure to
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...
. It begins with the oxidation of phenols by
polyphenol oxidase Polyphenol oxidase (PPO; also polyphenol oxidase i, chloroplastic), an enzyme involved in fruit browning, is a tetramer that contains four atoms of copper per molecule. PPO may accept monophenols and/or ''o''-diphenols as substrates. The ...
into
quinone The quinones are a class of organic compounds that are formally "derived from aromatic compounds uch as benzene or naphthalene">benzene.html" ;"title="uch as benzene">uch as benzene or naphthalene] by conversion of an even number of –CH= group ...
s, whose strong electrophilic state causes high susceptibility to a nucleophilic attack from other proteins. These quinones are then polymerized in a series of reactions, eventually resulting in the formation of brown pigments ( melanosis) on the surface of the food. The rate of enzymatic browning is reflected by the amount of active polyphenol oxidases present in the food. Hence, most research into methods of preventing enzymatic browning has been directed towards inhibiting polyphenol oxidase activity. However, not all browning of food produces negative effects. Examples of beneficial enzymatic browning: * Developing color and flavor in
coffee Coffee is a drink prepared from roasted coffee beans. Darkly colored, bitter, and slightly acidic, coffee has a stimulating effect on humans, primarily due to its caffeine content. It is the most popular hot drink in the world. Seeds of ...
,
cocoa bean The cocoa bean (technically cocoa seed) or simply cocoa (), also called the cacao bean (technically cacao seed) or cacao (), is the dried and fully Fermentation, fermented seed of ''Theobroma cacao'', from which cocoa solids (a mixture of non ...
s, and tea. * Developing color and flavor in dried fruit such as
fig The fig is the edible fruit of ''Ficus carica'', a species of small tree in the flowering plant family Moraceae. Native to the Mediterranean and western Asia, it has been cultivated since ancient times and is now widely grown throughout the world ...
s and
raisin A raisin is a dried grape. Raisins are produced in many regions of the world and may be eaten raw or used in cooking, baking, and brewing. In the United Kingdom, Ireland, New Zealand, and Australia, the word ''raisin'' is reserved for the ...
s. Examples of non-beneficial enzymatic browning: * Fresh fruit and vegetables, including
apple An apple is an edible fruit produced by an apple tree (''Malus domestica''). Apple trees are cultivated worldwide and are the most widely grown species in the genus '' Malus''. The tree originated in Central Asia, where its wild ancest ...
s,
potato The potato is a starchy food, a tuber of the plant ''Solanum tuberosum'' and is a root vegetable native to the Americas. The plant is a perennial in the nightshade family Solanaceae. Wild potato species can be found from the southern Uni ...
es,
banana A banana is an elongated, edible fruit – botanically a berry – produced by several kinds of large herbaceous flowering plants in the genus ''Musa''. In some countries, bananas used for cooking may be called "plantains", disting ...
s and
avocado The avocado (''Persea americana'') is a medium-sized, evergreen tree in the laurel family ( Lauraceae). It is native to the Americas and was first domesticated by Mesoamerican tribes more than 5,000 years ago. Then as now it was prized for ...
s. * Oxidation of polyphenols is the major cause of melanosis in crustaceans such as shrimp.


Control of enzymatic browning

The control of enzymatic browning has always been a challenge for the food industry. A variety of approaches are used to prevent or slow down enzymatic browning of foods, each method aimed at targeting specific steps of the chemical reaction. The different types of enzymatic browning control can be classified into two large groups: physical and chemical. Usually, multiple methods are used. The use of sulfites (powerful anti-browning chemicals) have been reconsidered due to the potential hazards that it causes along with its activity. Much research has been conducted regarding the exact types of control mechanisms that take place when confronted with the enzymatic process. Besides prevention, control over browning also includes measures intended to recover the food color after its browning. For instance, ion exchange filtration or ultrafiltration can be used in
winemaking Winemaking or vinification is the production of wine, starting with the selection of the fruit, its fermentation into alcohol, and the bottling of the finished liquid. The history of wine-making stretches over millennia. The science of wine and ...
to remove the brown color sediments in the solution.


Physical methods

*Heat treatment − Treating food with heat, such as blanching or
roasting Roasting is a cooking method that uses dry heat where hot air covers the food, cooking it evenly on all sides with temperatures of at least from an open flame, oven, or other heat source. Roasting can enhance the flavor through caramelizatio ...
, de-naturates enzymes and destroys the reactants responsible for browning. Blanching is used, for example, in
winemaking Winemaking or vinification is the production of wine, starting with the selection of the fruit, its fermentation into alcohol, and the bottling of the finished liquid. The history of wine-making stretches over millennia. The science of wine and ...
,
tea processing Tea processing is the method in which the leaves from the tea plant ''Camellia sinensis'' are transformed into the dried leaves for brewing tea. The categories of tea are distinguished by the processing they undergo. In its most general form, te ...
, storing nuts and
bacon Bacon is a type of salt-cured pork made from various cuts, typically the belly or less fatty parts of the back. It is eaten as a side dish (particularly in breakfasts), used as a central ingredient (e.g., the bacon, lettuce, and tomato sand ...
, and preparing vegetables for freezing preservation. Meat is often partially browned under high heat before being incorporated into a larger preparation to be cooked at a lower temperature which produces less browning. *Cold treatment − Refrigeration and
freezing Freezing is a phase transition where a liquid turns into a solid when its temperature is lowered below its freezing point. In accordance with the internationally established definition, freezing means the solidification phase change of a liquid ...
are the most common ways of storing food, preventing decay. The activity of browning enzymes, i.e., rate of reaction, drops in low temperatures. Thus, refrigeration helps to keep the initial look, color, and flavour of fresh vegetables and fruits. Refrigeration is also used during distribution and retailing of fruits and vegetables. *Oxygen elimination − Presence of oxygen is crucial for enzymatic browning, therefore eliminating oxygen from the environment helps to slow down the browning reaction. Withdrawing air or replacing it with other gases (e.g., N2 or CO2) during preservation, such as in vacuum-packaging or modified atmosphere packaging, wine or juice bottling, using impermeable films or edible
coating A coating is a covering that is applied to the surface of an object, usually referred to as the substrate. The purpose of applying the coating may be decorative, functional, or both. Coatings may be applied as liquids, gases or solids e.g. Pow ...
s, dipping into salt or sugar solutions, keeps the food away from direct contact with oxygen. Impermeable films made of plastic or other materials prevent food being exposed to oxygen in the air and avoid moisture loss. There is an increasing activity in developing packaging materials impregnated with
antioxidant Antioxidants are compounds that inhibit oxidation, a chemical reaction that can produce free radicals. This can lead to polymerization and other chain reactions. They are frequently added to industrial products, such as fuels and lubrica ...
s, antimicrobial, and
antifungal An antifungal medication, also known as an antimycotic medication, is a pharmaceutical fungicide or fungistatic used to treat and prevent mycosis such as athlete's foot, ringworm, candidiasis (thrush), serious systemic infections such as ...
substances, such as
butylated hydroxytoluene Butylated hydroxytoluene (BHT), also known as dibutylhydroxytoluene, is a lipophilic organic compound, chemically a derivative of phenol, that is useful for its antioxidant properties. BHT is widely used to prevent free radical-mediated oxidat ...
(BHT) and
butylated hydroxyanisole Butylated hydroxyanisole (BHA) is a synthetic, waxy, solid petrochemical. Its antioxidant properties have caused it to be widely used as a preservative in food, food packaging, animal feed, cosmetics, pharmaceuticals, rubber, and petroleum produ ...
(BHA), tocopherols, hinokitiol, lysozyme, nisin, natamycin, chitosan, and ε-polylysine. Edible coatings can be made of
polysaccharide Polysaccharides (), or polycarbohydrates, are the most abundant carbohydrates found in food. They are long chain polymeric carbohydrates composed of monosaccharide units bound together by glycosidic linkages. This carbohydrate can react with w ...
s,
protein Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residues. Proteins perform a vast array of functions within organisms, including catalysing metabolic reactions, DNA replication, res ...
s,
lipid Lipids are a broad group of naturally-occurring molecules which includes fats, waxes, sterols, fat-soluble vitamins (such as vitamins A, D, E and K), monoglycerides, diglycerides, phospholipids, and others. The functions of lipids in ...
s, vegetable skins, plants or other natural products. *Irradiation −
Food irradiation Food irradiation is the process of exposing food and food packaging to ionizing radiation, such as from gamma rays, x-rays, or electron beams. Food irradiation improves food safety and extends product shelf life (preservation) by effective ...
using UV-C,
gamma rays A gamma ray, also known as gamma radiation (symbol γ or \gamma), is a penetrating form of electromagnetic radiation arising from the radioactive decay of atomic nuclei. It consists of the shortest wavelength electromagnetic waves, typically ...
,
x-ray An X-ray, or, much less commonly, X-radiation, is a penetrating form of high-energy electromagnetic radiation. Most X-rays have a wavelength ranging from 10 picometers to 10  nanometers, corresponding to frequencies in the range 30&nb ...
s, and
electron beam Cathode rays or electron beam (e-beam) are streams of electrons observed in discharge tubes. If an evacuated glass tube is equipped with two electrodes and a voltage is applied, glass behind the positive electrode is observed to glow, due to el ...
s is another method to extend the food shelf life.
Ionizing radiation Ionizing radiation (or ionising radiation), including nuclear radiation, consists of subatomic particles or electromagnetic waves that have sufficient energy to ionize atoms or molecules by detaching electrons from them. Some particles can travel ...
inhibits the vitality of microorganisms responsible for food spoilage and delays the maturation and
sprouting Sprouting is the natural process by which seeds or spores germinate and put out shoots, and already established plants produce new leaves or buds, or other structures experience further growth. In the field of nutrition, the term signifies ...
of preserving vegetables and fruits.


Chemical methods

*Acidification − Browning enzymes, as other enzymes, are active at a specific range of pH. For example, PPO shows optimal activity at pH 5-7 and is inhibited below pH 3. Acidifying agents and
acidity regulator Acidity regulators, or pH control agents, are food additives used to change or maintain pH (acidity or basicity). They can be organic or mineral acids, bases, neutralizing agents, or buffering agents. Typical agents include the following acids ...
s are widely used as
food additive Food additives are substances added to food to preserve Taste, flavor or enhance taste, appearance, or other sensory qualities. Some additives have been used for centuries as part of an effort to preserve food, for example vinegar (pickling), sal ...
s to maintain a desired pH in food products.
Acidulant Acidulants are chemical compounds that give a tart, sour, or acidic flavor to foods or enhance the perceived sweetness of foods. Acidulants can also function as leavening agents and emulsifiers in some kinds of processed foods.Berry, S.K.. (2001). R ...
s, such as
citric acid Citric acid is an organic compound with the chemical formula HOC(CO2H)(CH2CO2H)2. It is a colorless weak organic acid. It occurs naturally in citrus fruits. In biochemistry, it is an intermediate in the citric acid cycle, which occurs in ...
,
ascorbic acid Vitamin C (also known as ascorbic acid and ascorbate) is a water-soluble vitamin found in citrus and other fruits and vegetables, also sold as a dietary supplement and as a topical 'serum' ingredient to treat melasma (dark pigment spots) ...
, and glutathione, are used as anti-browning agents. Many of these agents also show other anti-browning effects, such as chelating and antioxidant activities. *Antioxidants − Many
antioxidant Antioxidants are compounds that inhibit oxidation, a chemical reaction that can produce free radicals. This can lead to polymerization and other chain reactions. They are frequently added to industrial products, such as fuels and lubrica ...
s are used in food industry as food additives. These compounds react with oxygen and suppress the initiation of the browning process. Also, they interfere with intermediate products of the following reactions and inhibit
melanin Melanin (; from el, μέλας, melas, black, dark) is a broad term for a group of natural pigments found in most organisms. Eumelanin is produced through a multistage chemical process known as melanogenesis, where the oxidation of the amino ...
formation.
Ascorbic acid Vitamin C (also known as ascorbic acid and ascorbate) is a water-soluble vitamin found in citrus and other fruits and vegetables, also sold as a dietary supplement and as a topical 'serum' ingredient to treat melasma (dark pigment spots) ...
, N-acetylcysteine, L-cysteine, 4-hexylresorcinol,
erythorbic acid Erythorbic acid (isoascorbic acid, D-araboascorbic acid) is a stereoisomer of ascorbic acid (vitamin C). It is synthesized by a reaction between methyl 2-keto-D-gluconate and sodium methoxide. It can also be synthesized from sucrose or by strai ...
, cysteine hydrochloride, glutathione are examples of antioxidants that have been studied for their anti-browning properties. *Chelating agents − Polyphenol oxidase requires
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
as a cofactor for its functionality, thus copper-
chelating agent Chelation is a type of bonding of ions and molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single central metal atom. These ligands a ...
s inhibit the activity of this enzyme. Many agents possessing chelating activity have been studied and used in different fields of food industry, such as
citric acid Citric acid is an organic compound with the chemical formula HOC(CO2H)(CH2CO2H)2. It is a colorless weak organic acid. It occurs naturally in citrus fruits. In biochemistry, it is an intermediate in the citric acid cycle, which occurs in ...
, sorbic acid, polyphosphates, hinokitiol, kojic acid, EDTA, porphyrins, polycarboxylic acids, different proteins. Some of these compounds also have other anti-browning effects, such as acidifying or antioxidant. Hinokitiol is used in coating materials for
food packaging Food packaging is a packaging system specifically designed for food and represents one of the most important aspects among the processes involved in the food industry, as it provides protection from chemical, biological and physical alteratio ...
.


Other methods

*Natural agents − Different natural products and their extracts, such as
onion An onion (''Allium cepa'' L., from Latin ''cepa'' meaning "onion"), also known as the bulb onion or common onion, is a vegetable that is the most widely cultivated species of the genus '' Allium''. The shallot is a botanical variety of the on ...
,
pineapple The pineapple (''Ananas comosus'') is a tropical plant with an edible fruit; it is the most economically significant plant in the family Bromeliaceae. The pineapple is indigenous to South America, where it has been cultivated for many centuri ...
, lemon, and
white wine White wine is a wine that is Fermentation in winemaking, fermented without skin contact. The wine color, colour can be straw-yellow, yellow-green, or yellow-gold. It is produced by the alcoholic fermentation of the non-coloured Juice vesicles, ...
, are known to inhibit or slow the browning of some products. Onion and its extract exhibit potent anti-browning properties by inhibiting the PPO activity. Pineapple juice have shown to possess anti-browning effect on apples and bananas. Lemon juice is used in making doughs to make the
pastry Pastry is baked food made with a dough of flour, water and shortening (solid fats, including butter or lard) that may be savoury or sweetened. Sweetened pastries are often described as '' bakers' confectionery''. The word "pastries" suggests ...
products look brighter. This effect is possibly explained by the anti-browning properties of citric and
ascorbic acid Vitamin C (also known as ascorbic acid and ascorbate) is a water-soluble vitamin found in citrus and other fruits and vegetables, also sold as a dietary supplement and as a topical 'serum' ingredient to treat melasma (dark pigment spots) ...
s in the lemon juice. *Genetic modification − Arctic apples have been genetically modified to silence the expression of PPO, thereby delaying the browning effect, and improving apple eating quality.


Non-enzymatic browning

The second type of browning, non-enzymatic browning, is a process that also produces the brown pigmentation in foods but without the activity of enzymes. The two main forms of non-enzymatic browning are caramelization and the
Maillard reaction The Maillard reaction ( ; ) is a chemical reaction between amino acids and reducing sugars that gives browned food its distinctive flavor. Seared steaks, fried dumplings, cookies and other kinds of biscuits, breads, toasted marshmallows, and m ...
. Both vary in the reaction rate as a function of water activity (in food chemistry, the standard state of water activity is most often defined as the partial vapor pressure of pure water at the same temperature). Caramelization is a process involving the
pyrolysis The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements '' ...
of
sugar Sugar is the generic name for sweet-tasting, soluble carbohydrates, many of which are used in food. Simple sugars, also called monosaccharides, include glucose, fructose, and galactose. Compound sugars, also called disaccharides or do ...
. It is used extensively in cooking for the desired nutty flavor and brown color. As the process occurs, volatile chemicals are released, producing the characteristic
caramel Caramel ( or ) is an orange-brown confectionery product made by heating a range of sugars. It can be used as a flavoring in puddings and desserts, as a filling in bonbons, or as a topping for ice cream and custard. The process of carameli ...
flavor. The other non-enzymatic reaction is the
Maillard reaction The Maillard reaction ( ; ) is a chemical reaction between amino acids and reducing sugars that gives browned food its distinctive flavor. Seared steaks, fried dumplings, cookies and other kinds of biscuits, breads, toasted marshmallows, and m ...
. This reaction is responsible for the production of the flavor when foods are cooked. Examples of foods that undergo Maillard reaction include breads, steaks, and potatoes. It is a chemical reaction that takes place between the amine group of a free
amino acid Amino acids are organic compounds that contain both amino and carboxylic acid functional groups. Although hundreds of amino acids exist in nature, by far the most important are the alpha-amino acids, which comprise proteins. Only 22 alpha ...
and the carbonyl group of a reducing sugar, usually with the addition of heat. The sugar interacts with the amino acid, producing a variety of odors and flavors. The Maillard reaction is the basis for producing artificial flavors for processed foods in the flavoring industry since the type of amino acid involved determines the resulting flavor. Melanoidins are brown, high molecular weight heterogeneous polymers that are formed when sugars and amino acids combine through the Maillard reaction at high temperatures and low water activity. Melanoidins are commonly present in foods that have undergone some form of non-enzymatic browning, such as barley malts (Vienna and Munich), bread crust, bakery products and coffee. They are also present in the wastewater of sugar refineries, necessitating treatment in order to avoid contamination around the outflow of these refineries.


Browning of grapes during winemaking

Like most fruit, grapes vary in the number of phenolic compounds they have. This characteristic is used as a parameter in judging the quality of the wine. The general process of winemaking is initiated by the enzymatic oxidation of phenolic compounds by polyphenol oxidases. Contact between the phenolic compounds in the
vacuole A vacuole () is a membrane-bound organelle which is present in plant and fungal cells and some protist, animal, and bacterial cells. Vacuoles are essentially enclosed compartments which are filled with water containing inorganic and organic m ...
of the grape cell and the
polyphenol oxidase Polyphenol oxidase (PPO; also polyphenol oxidase i, chloroplastic), an enzyme involved in fruit browning, is a tetramer that contains four atoms of copper per molecule. PPO may accept monophenols and/or ''o''-diphenols as substrates. The ...
enzyme Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products ...
(located in the
cytoplasm In cell biology, the cytoplasm is all of the material within a eukaryotic cell, enclosed by the cell membrane, except for the cell nucleus. The material inside the nucleus and contained within the nuclear membrane is termed the nucleoplasm. ...
) triggers the oxidation of the grape. Thus, the initial browning of grapes occurs as a result of "compartmentalization modification" in the cells of the grape.


Implications in food industry and technology

Enzymatic browning affects the color, flavor, and nutritional value of foods, causing huge economic loss when not sold to consumers on time. It is estimated that more than 50% of produce is lost as a result of enzymatic browning. The increase in human population and consequential depletion in natural resources has prompted many biochemists and food engineers alike to find new or improved techniques to preserve food and for longer by using methods to inhibit the browning reaction. This effectively increases the shelf life of foods, solving this part of the waste problem. A better understanding of the enzymatic browning mechanisms, specifically, understanding the properties of the enzymes and substrates that are involved in the reaction may help food technologists to control certain stages in the mechanism and ultimately apply that knowledge to inhibit browning. Apples are fruits commonly studied by researchers due to their high phenolic content, which make them highly susceptible to enzymatic browning. In accordance with other findings regarding apples and browning activity, a correlation has been found between higher phenolic quantities and increased enzymatic activity in apples. This provides a potential target and thus hope for food industries wishing to genetically modify foods to decrease polyphenol oxidase activity and thus decrease browning. An example of such accomplishments in food engineering is in the production of Arctic apples. These apples, engineered by ''Okanagan Specialty Fruits Inc,'' are a result of applying gene splicing, a laboratory technique that has allowed for the reduction in polyphenol oxidase. Another type of issue that is closely studied is the browning of seafood.
Seafood Seafood is any form of sea life regarded as food by humans, prominently including fish and shellfish. Shellfish include various species of molluscs (e.g. bivalve molluscs such as clams, oysters and mussels, and cephalopods such as octopus an ...
, in particular shrimp, is a staple consumed by people all over the world. The browning of shrimp, which is actually referred to as melanosis, creates a great concern for food handlers and consumers. Melanosis mainly occurs during postmortem handling and refrigerated storage. Recent studies have found a plant extract that acts as an anti-melatonin polyphenol oxidase inhibitor serves the same function as sulfites but without the health risks.


See also

* Browning (partial cooking) *
Decomposition Decomposition or rot is the process by which dead organic substances are broken down into simpler organic or inorganic matter such as carbon dioxide, water, simple sugars and mineral salts. The process is a part of the nutrient cycle and ...
*
Gravy Gravy is a sauce often made from the juices of meats that run naturally during cooking and often thickened with wheat flour or corn starch for added texture. The gravy may be further coloured and flavoured with gravy salt (a simple mix of sa ...
* Water activity


References

{{Food preservation Food science Biochemistry pl:Ciemnienie nieenzymatyczne