F Food chemistry

F1 Food groups
Food – ‘Any substance, whether processed, semi-processed or raw, which is intended for human consumption, and includes drink, chewing gum and any substance which has been used in the manufacture, preparation or treatment of ‘food’, but does not include cosmetics or tobacco or substances used only as drugs’ – Codex Alimentarius (FAO/WHO) definition 2005.

Learning objectives

• •

Distinguish between a food and a nutrient Describe the chemical composition of lipids, carbohydrates and proteins

Nutrients
A nutrient is any substance obtained from food and used by the body to provide energy, to regulate growth or to maintain and repair the body’s tissues. Any item of food will contain at least one, and possibly many, different types of nutrient. For example, bread is food and contains several nutrients including carbohydrates, proteins and lipids. Any substance that does not contain usable nutrients is not food. There are seven principal classes of nutrient: • carbohydrate • protein • lipid (fats and oils) • minerals • vitamins • water • bre is sometimes included because, although it is not absorbed by the body, it is required for the maintenance of a properly functioning intestinal tract.

Examiner’s tip The words lipid and fat may be used interchangeably in many texts and exam questions.

Carbohydrate
Carbohydrates contain only the elements carbon, hydrogen and oxygen. The most basic carbohydrates, which are often referred to as simple sugars, are called monosaccharides. Examples of monosaccharides include glucose, fructose and galactose. They contain carbon, hydrogen and oxygen in the ratio 1 : 2 :1 and therefore can be represented by the empirical formula CH2O. Monosaccharides can exist in two structural forms: linear or cyclic (Figure F1). In the cyclic form, the carbonyl group is broken to produce an intramolecular oxygen bridge (see Figure F1). The hydroxyl groups remain unchanged. In the linear form, monosaccharides contain a carbonyl group (C=O) as part of either an aldehyde (e.g. glucose) or a ketone (e.g. fructose) and at least two hydroxyl (alcohol) –OH groups. Monosaccharides can be combined to produce more complex carbohydrates such as disaccharides, e.g. sucrose and maltose (Figure F2)
CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011

The structure of carbohydrates is discussed in more detail in Option B, page 11 on the CD-ROM.

In solution, the cyclic form of a monosaccharide predominates, with only a small fraction existing as the linear structure.

F FOOD CHEMISTRY

1

Fischer projection is a twodimensional representation of a three-dimensional molecule. In the projected structure, horizontal bonds represent groups pointing towards the viewer and vertical bonds represent groups pointing away from the viewer.

a H C H HO H H C C C C

O CH2OH OH H OH OH HO H H C O C C C H OH OH

b CH2OH H C HO C H OH C H O H C OH OH C H

CH2OH

CH2OH

Figure F1 (a) The chemical structures of glucose (left) and fructose (right) in Fischer projection; (b) a cyclic form of glucose.

The structures of polysaccharides are discussed in Option B, page 12 on the CD-ROM.

and polysaccharides (e.g. starch and cellulose). When monosaccharides are joined together, they release a molecule of water in a condensation reaction. The bond formed between the monomers is called a glycosidic bond and contains another oxygen atom that bridges the gap between two monosaccharide units.
CH2OH H HO O H OH H H OH H O H CH2OH O H OH H H OH OH H

Figure F2 A molecule of the disaccharide sugar maltose.

Protein
Some proteins also contain the element sulfur. Protein always contains the elements carbon, hydrogen, oxygen and nitrogen. Proteins are polymers of smaller sub-units called amino acids (or, more precisely, 2-amino acids). The smallest protein (called a dipeptide) contains just 2 amino acids but many proteins contain thousands of amino acids. Amino acids contain an amine group (NH2) at one end and a carboxylic acid group (COOH) at the other. The central carbon contains a bond to a variable group, R (Figure F3). Amino acids are sometimes referred to as 2-amino acids to indicate that the amine group is on the second carbon of the carboxylic acid (position 1) main chain. When two amino acids join together in a condensation reaction (water eliminated) they form a peptide bond which contains the amide (CONH) functional group (Figure F3).

The structure of proteins is discussed in more detail in Option B, page 2 on the CD-ROM.

Lipids
Lipids contain only the elements carbon, hydrogen and oxygen. Lipids may be split into two classes: oils (usually from plant sources and liquids at room temperature) and fats (usually from animal sources and solids at room temperature).
a H N H R C H C O H HO b O O C H C CH2 N H H c H H N H C H O C H N H C H C OH O

SH Figure F3 (a) The general structure of an amino acid; (b) the sulfur-containing amino acid methionine; (c) a dipeptide molecule containing a peptide bond.

peptide bond

2

F FOOD CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011

ester groups

long hydrocarbon chain

H

O

H H H H H H H H H H H H H H H C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H H

H C O O H C O O H C O H

Lipids are triester molecules, formed by reacting three longchain fatty acid molecules with the three hydroxyl (–OH) groups of a glycerol (propane-1,2,3triol) molecule. The resultant compounds are often referred to as triglycerides (Figure F4).

Figure F4 The structure of a triglyceride molecule.

Test yourself
1 Give the molecular formula of the molecule, X, shown and explain to which food group it belongs.
CH2OH H HO O H OH H H OH H OH

2 The molecule in Question 1 can react with another molecule in a condensation reaction to form the compound, Y, below. Work out the molecular formula of Y and give the structure of the molecule, Z, that must react with X to form Y.
CH2OH H HO O H OH H H OH H HOCH2 H O OH H O HO CH2OH H

F2 Fats and oils
The long-chain fatty acids that make up the bulk of the mass of a triglyceride molecule may be divided into two categories: (a) saturated (b) unsaturated, which can be further subdivided into: (i) mono-unsaturated (ii) poly-unsaturated

Learning objectives

• •

The structure of fatty acids
Saturated
Saturated fatty acids are those in which the carbon atoms are joined together only by C–C single bonds. Saturated fatty acids therefore contain the maximum number of hydrogen atoms in the carbon chain. For example, stearic acid is a saturated fatty acid (Figure F5). It contains a carboxylic acid functional group and an alkane-like (saturated) hydrocarbon chain.
O H H H H H H H H H H H H H H H H H H O C C C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H H H H Figure F5 Stearic acid (C17H35COOH).

Describe the structure of saturated and mono-unsaturated fatty acids and understand how structure affects melting point Deduce the stability of a lipid from its structure Describe the hydrogenation of unsaturated fats and its advantages and disadvantages

CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011

F FOOD CHEMISTRY

3

Unsaturated
Unsaturated fatty acids contain one (mono-unsaturated) or several (poly-unsaturated) C=C double bonds. They therefore do not contain the maximum number of hydrogen atoms in the carbon chain. In a typical, naturally occurring lipid (oil or fat), there will be a mixture of saturated, mono-unsaturated and poly-unsaturated fatty acids (Figure F6). For example, butterfat (the main fat found in cow’s milk) contains predominantly saturated fatty acids. Table F1 compares the composition of butterfat to olive oil and sunflower oil, which are both derived from plants.
a HO b HO c HO Figure F6 (a) Elaidic acid; (b) linoleic acid; (c) arachidonic acid. O

O

O

Butterfat % saturated % mono-unsaturated % poly-unsaturated 65 30 5

Olive oil 15 70 15

Sunflower oil 10 20 70

Table F1 Approximate fatty acid content of animal and plant lipids.

Fats and oils are categorised according to the predominant type of fatty acid present. Thus butterfat is classed as saturated, olive oil as monounsaturated and sunflower oil would be classed as poly-unsaturated.

Solid or liquid?
In general, saturated fatty acids will tend to be solid at room temperature, while mono- and poly-unsaturated ones will remain liquid. Lipid-rich foods can have very different physical properties. For example, beef dripping is a solid at room temperature but vegetable oil stays liquid even when placed in the fridge. The reason for this difference depends mainly on the structure of the fatty acids that make up the predominant triglyceride in the food.

Degree of crystallisation
Degree of crystallisation is another way of describing the property of solidification (i.e. how likely a substance is to be a solid) and is directly related to a fat’s melting point. There are three main factors that affect the melting point of a fat: relative molecular mass (length of fatty acid chains), degree of unsaturation and nature of the double bonds (cis or trans).

4

F FOOD CHEMISTRY

CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011

and poly-unsaturated fatty acids generally have lower melting points than saturated fatty acids of similar relative molecular mass. whereas in the trans form they are positioned on opposite sides.and poly-unsaturated fatty acids. because the double bond(s) causes many of them to adopt a ‘kinked’ or ‘curled’ structure (see Figure F7). and hence the lower the melting point.6 °C whereas lauric acid (C12H24O2 – Mr 200) melts at 44. Longer chain fatty acids tend to be solid at room temperature.g.2 °C – both are saturated. H C H3C cis-but-2-ene H H3C C H C CH3 H C CH3 trans-but-2-ene Name of food butter lard shortening palm (oil) coconut (oil) olive oil peanut oil safflower oil sunflower oil corn oil cod liver oil linoleic acid linolenic acid Predominant type of fatty acid saturated saturated saturated saturated saturated State at room Approximate temperature melting point / °C solid solid solid solid solid 35 30 45 37 26 0 −2 −10 −17 −17 −11 −5 −5 −11 mono-unsaturated liquid mono-unsaturated liquid poly-unsaturated poly-unsaturated poly-unsaturated poly-unsaturated poly-unsaturated poly-unsaturated liquid liquid liquid liquid liquid liquid canola (rapeseed) oil mono-unsaturated liquid Table F2 Degree of saturation and approximate melting points of various lipids. increasing the relative molecular mass of a fatty acid will increase its melting point. The rise in melting point as the chain gets longer is due to an increase in the number and combined strength of the intermolecular van der Waals’ interactions along the length of the chains.Effect of relative molecular mass All other things being equal. In the cis form the hydrogens are both on the same side of the double bonds. this is why oils are a source of mono. Mono. These represent two different arrangements of the hydrogens attached to the carbons in the double bond. Some examples of saturated and unsaturated lipids are shown in Table F2. Effect of unsaturation Unsaturation (C=C bonds) in the hydrocarbon chain decreases the degree of crystallisation of lipids and they are more likely to be oils.e. the more unsaturated the molecule) the more distorted the chain will become. Effect of geometrical isomerism Unsaturated fatty acids can exist in two forms: cis and trans. The greater the number of double bonds (i. stearic acid (C18H36O2 – Mr 284) melts at 69. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 5 . e.

For example. which are kinked or bent and have a reduced number of potential contact points (Figure F7). in the presence of light (photo-oxidation) and with enzymes/heat/water (hydrolysis). a trans double bond b c H O H C O C O C cis double bond O C H O H C O C H Figure F7 (a) Trans double bonds: chain is fairly straight. Oxidation with atmospheric oxygen (auto-oxidation) Fats will go rancid even when kept at low temperatures. 6 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . They go rancid at a slower rate. Saturated fats are more stable than unsaturated fats. Stability In general. This is due to the reactivity of the C=C double bond(s) present in the latter two. thus the strength of van der Waals’ interactions is greater. this is due to their reaction with oxygen in the air causing them to break down into a mixture of unpleasant-tasting compounds including hydrocarbons. Choice of fat for purpose Fats and oils are chosen for cooking on the basis of their melting temperature. the carbon chain remains straight and so contact points between chains are maximised. oils and other lipids undergo chemical decomposition. Rancidi cation is the process by which fats. The absence of a reactive functional group in saturated fatty acids renders them fairly inert. This means that trans fatty acids have a higher melting point than their cis isomers. fats that contain predominantly saturated fatty acids are more stable than those classified as mono. reaction with hydrogen (hydrogenation).or poly-unsaturated. (c) cis double bonds cause the chains to be kinked and molecules cannot pack together as well. cocoa butter melts at close to body temperature making it ideal for creating ‘melt-in-the-mouth’ chocolates. (b) cis double bond causes a kink in the chain. The C=C double bond in unsaturated fats may undergo a number of reactions: reaction with oxygen (auto-oxidation).In the trans isomer. fats chosen for cake-making melt over a wide range of temperatures to provide different baking properties and texture of the final product.

cis fatty acids can isomerise into the trans form. Photo-oxidation (reaction in light) This is another free-radical-based reaction similar to auto-oxidation. for example. more usually. margarine. Disadvantages of hydrogenation Clinical evidence points to health benefits from a diet containing more mono. Finally. Hydrogenation In this process. F FOOD CHEMISTRY 7 . the faster the rate of oxidation. in the hydrogenation process.or. In addition. The body finds it difficult to metabolise trans fatty acids (lipase enzymes seem to recognise only cis forms) and so they tend to accumulate in the adipose (fatty) tissue rather than be excreted. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 An enzyme is a biological catalyst that speeds up a specific biochemical reaction. the percentage saturation can be varied to yield partially hydrogenated products with different physical properties and uses. Hydrolysis (reaction with water. Generally. heat and enzymes) Hydrolysis involves splitting a molecule into smaller pieces using water. Enzymes are proteins with a unique threedimensional structure. hydrogen gas is added across the double bond(s) present in mono. the more unsaturated fatty acids present in a fat. In the presence of high light intensities.aldehydes and ketones. Water is able to cleave the ester bonds in a triglyceride between the fatty acids and the glycerol backbone. fats will oxidise and go rancid far more quickly than by auto-oxidation alone. the degree of saturation in the hydrogenated product is not 100% and. The mechanism involves the production of highly reactive free radical species. rather than joined together in a triglyceride. Saturated fats are more damaging to the heart and circulatory system. These have been implicated in a number of cardiovascular diseases. Advantages of hydrogenation Partially hydrogenated vegetable oils are cheaper to produce than saturated fats from animals. This chemical reaction occurs when the fat is heated with acid or alkali. i. Hydrogenation also increases hardness and plasticity (stiffness) of the products. the greater the number of double bonds present.e. This will yield the triol (glycerol) and the original fatty acids (see Figure F8 on page 10). and they also have an increased shelf life over their fully unsaturated precursors as the rate of oxidation decreases with increased saturation.and poly-unsaturated fats than saturated. Hydrogenation is also used to produce other semi-solid fats used for baking. Generally. trans fats are a poorer quality source of energy compared to their cis counterparts. It can also be catalysed by enzymes such as lipases. zinc or copper catalyst. Trans fatty acids also cause an increase in more harmful forms of circulating cholesterol such as low density lipoprotein (LDL). The release of fatty acids when fats undergo hydrolysis is one reason that fats can develop an unpleasant smell when they go rancid. poly-unsaturated vegetable oils at a high temperature (140–225 °C) and pressure in the presence of a nickel. In the body this process is used in the digestion of fats and oils as fatty acids are more easily absorbed as separate units. by carefully controlling the conditions. This increases the saturated character of a fat (partial hydrogenation) and is used to turn liquid vegetable oils into semi-solid or solid fats.

• • • • Understand the factors that affect the shelf life of a food Describe hydrolytic and oxidative rancidity of fats and how they can be reduced Describe traditional methods for extending shelf life Discuss natural and synthetic antioxidants including their structural features. These preserved foods are. Changes in water content can also increase the rate of non-enzymatic and enzymatic browning of food (the process in which foods literally turn the colour brown).g. proteins and starch. sources. mono-unsaturated or poly-unsaturated. Changes in water content can also result in degradation of nutrients such as vitamins. advantages and disadvantages of use Factors affecting shelf life and food quality Several factors affect the shelf life and quality of food. In most supermarkets.Test yourself 3 The formulas of some fatty acids are shown below. C15H23COOH C13H27COOH C19H35COOH C17H33COOH 4 Arrange the following fatty acids in order of increasing melting point (lowest first). changes in pH). Deduce the number of C=C bonds in each and classify them as saturated. if breakfast cereal absorbs water it becomes less crisp). vegetables and seafood. ‘best before’ dates are displayed clearly on packaging. There are several other reasons why changes in water content affect the shelf life of food. which is undesirable in foods such as fruits. Bacteria find it easier to multiply in foods containing higher quantities of water – drying or salting foods can increase their shelf life by reducing water content. These indicate the supermarket or manufacturer’s estimate of the food’s shelf life. light. These include water content. chemical changes (e. Many items of food may still be edible beyond this date. but the food will not be in its optimum state. texture and appearance. C19H39COOH C17H35COOH C17H31COOH Learning objectives F3 Shelf life Shelf life is the period of time for which a food retains the desired qualities expected by the consumer. 8 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . Shelf life is different to the ‘expiration’ or ‘use by’ dates. however. after which a food product may become harmful. Once a food’s shelf life has been exceeded it is considered unsuitable for human consumption due to changes in the properties described above as well as the potential for microbial spoilage.g. such as avour. particularly vulnerable to bacterial spoilage should they absorb moisture. temperature and contact with air. The rate of these processes is a maximum at an intermediate level of water content. The abundance of water increases the rate of hydrolysis and can lead to rancidity (due to hydrolysis of fats). Water content Changes in the water content can alter the texture of food (e.

Temperature Raised temperatures generally act to increase the rate at which processes such as hydrolysis. Name of fatty acid Substance(s) detected in butanoic acid hexanoic acid octanoic acid palmitic acid oleic acid stearic acid lauric acid milk. Rancidity will be manifest as disagreeable changes in taste. dry environment such as a pantry or fridge helps to alleviate the effect of raised temperature. lard oil. smell. Both high and low pH levels can increase the speed at which proteins. starches and vitamins are degraded. Appropriate packaging should be used to reduce exposure of the food to light. acrid oil. colour and texture. Light Light can cause rancidity in fats by the process of photo-oxidation (see page 7). CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 9 .g. photo-oxidation and microbial growth occur. Light is also able to bleach the natural dyes present in many foods. cocoa butter substitutes Characteristic smell/taste vomit goats. Contact with air Auto-oxidation of fats and other compounds such as alcohols occurs spontaneously in the presence of atmospheric oxygen. those flavours that we perceive as unpleasant. changes to the pH and chemical balance of a food will change its flavour. Fats turn rancid. farmyard animals musty. causing them to degrade more rapidly and rendering them less useful. causing colours to fade. while the ethanol in alcoholic beverages will be slowly converted to ethanoic acid by oxidation: C2H5OH + O2 → CH3COOH + H2O Rancidity Rancidity is a descriptive term relating to our perception of the flavour of fats and oils: specifically. fat soap Table F3 Various ‘off-smelling’ naturally occurring fatty acids and their associated odours. changes in the chemical composition of foods can lead to increased rate of hydrolysis. Exposure to high light levels can also lead to chemical changes in many of the common vitamins. pH In a similar manner to increased water content. e. thus reducing the shelf life of products. indicating a food has gone off or is starting to spoil. soap wax. Keeping food in a cool. Additionally. texture and appearance (Table F3). butter milk milk chocolate chocolate chocolate palm/coconut oil.Chemical changes.

Packaging Inert gas Filling packaging with an inert gas to expel atmospheric oxygen reduces the rate of auto. H H H H C C C H triglyceride O O O O C O C O C C17H35 C17H35 C17H35 + 3H2O H H H H C C C H glycerol fatty acid OH OH + 3C17H35COOH OH Figure F8 The hydrolysis of a triglyceride to yield one molecule of glycerol and three molecules of fatty acid. The greater the degree of unsaturation present. Decreasing exposure to light by storing food in a dark environment (e. Processing Low temperature storage/refrigeration reduces the rate of lipasecatalysed hydrolysis. crystallising (adding sugar) and smoking decreases the effects of hydrolysis and microbial spoilage. particularly in dairy products. Oxidative rancidity The fatty acid chains liberated by hydrolysis can undergo oxidation via auto. the extremely high temperatures and presence of water in foods can lead to rapid rancidification. Oily fish. The process can be speeded up by increased water content. Classic examples include filling packets of crisps (US: chips) and other snack foods with nitrogen. The lipase enzyme works best at its optimum temperature of around 37 °C. which contain polyunsaturated fatty acids such as eicosapentaenoic acid (EPA) with five C=C double bonds.and photo-oxidation in a free radical chain reaction.Hydrolytic rancidity This is the process by which fats and oils are broken down into their constituent fatty acids and glycerol (Figure F8). are particularly susceptible to rancidification. oxygen adds across C=C double bonds of unsaturated fatty acids and causes them to break down into unpleasant smelling and tasting volatile compounds such as ketones. During deep-fat frying. enzymes may also catalyse the mechanism.g.g. the more predisposed a lipid will be to oxidative rancidification. like mackerel and herring. or by using coloured glass for storage vessels will reduce the rate of adverse photochemical reactions. the presence of enzymes (e. high (OH−) or low (H+) pH values and raised temperatures. 10 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 .and photo-oxidation. in a cupboard or pantry). Reducing moisture content by using methods such as salting. These include processing the food. Preventing rancidification and increasing shelf life Various techniques can be employed to reduce the rate at which lipids become rancid. In this process. careful choice of packaging and adding additives. lipase). aldehydes as well as some alcohols.

The jelly formed prevents the growth of bacteria and moulds. as well as large amounts of sugar. propanoic acid (C2H5COOH). Other jellied preserves may use a gelling agent like aspic (e. are produced by boiling fruits to kill off microbes and then adding a gelling agent. pickled eggs and onions. Ethanoic acid (CH3COOH) and benzoic acid prevent mould and bacterial growth in pickled meat and fish products. NaNO3. The Spanish delicacy bacalao is cod fish preserved by salting. They also add to the flavour.Hermetic sealing Using a film packaging around the food. Brine and vinegar are classic pickling solutions as bacteria and mould find it extremely difficult to multiply in the presence of these solutions. Adding additives Sodium sul te (Na2SO3). a H C HC3 H C O C b H3C CH2 O C OH The sulfite.Vinegar is a solution of ethanoic acid. yeasts and other moulds (Figure F10). citric acid is often used to preserve soft drinks. Traditional methods for extending shelf life Fermentation is used to increase shelf life of certain foods such as sauerkraut. Sodium benzoate (C6H5COONa) and benzoic acid (C6H5COOH) are used as preservatives preventing the growth of microbes in fruit juices. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 H3C H C OH O C OH Figure F11 Lactic acid (2-hydroxy propanoic acid). Pickling increases the shelf life of foods by keeping them in a liquid environment that is inherently antimicrobial. NO2−. O OH Figure F9 Benzoic acid. Preserves (e. carbonated drinks and pickled foods (Figure F9). sodium and calcium propanoate (C2H5COONa and (C2H5COO)2Ca) can be added to bread and cheese to delay the growth of bacteria. rancidification and microbial growth. prevent the growth of bacteria and moulds and also as colour fixatives. prevents it from coming into contact with oxygen in the air. jellied eels). the cell membrane). ion is also called the nitrate(III) ion. sodium hydrogensul te (NaHSO3) and citric acid are added to foods as oxygen scavengers and help to prevent non-enzymatic browning. C C OH H H Figure F10 (a) Sorbic acid. The nitrite. Reducing the quantity of air present at the top of the vessel will decrease the rate of oxidation. ion is also called the sulfate(IV) ion. SO32−. Minimising the amount of air present This is used especially in bottled and canned foods. Examples include gherkins. Salting is an ancient and highly successful preservation technique which involves reducing the water content of foods (by osmosis) and thereby decreasing the rates of hydrolysis.g. Most fresh meat tends to be sold in hermetically sealed packaging. Sodium and potassium nitrite and nitrate (NaNO2.g. dry sausages (salamis) and yogurt by using bacteria to break down the sugars present creating lactic acid which acts as the preservative. Osmosis is the passive process by which water moves from a region of low solute concentration (dilute solution) to a region of high solute concentration. such as pectin. F FOOD CHEMISTRY 11 . through a partially permeable membrane (e. Sorbic acid (C5H7COOH). The high sugar content also helps to reduce microbial growth by reducing available water. (b) propanoic acid. KNO3) are used to cure meat and fish. Low-gas-permeability film can be used as an alternative. The sulfites are commonly added to fresh meat and dried fruit.g. KNO2. jams).

The structures of some synthetic antioxidants are shown in Table F4. The phenol group is common to all these compounds (Figure F15). grains. Antioxidants Antioxidants are substances that delay the onset or slow down the process of oxidation. tomato. Vitamin C (ascorbic acid) HO HO HO H O O OH Vitamin C (Figure F12) is found in high levels in citrus fruits. nuts. pumpkin. They also work by reducing the water content of foods. sweet potato. β-carotene is found in high quantities in carrots. green-leaf vegetables.Drying and smoking are other techniques with a long heritage. O CH3 CH3 CH3 CH3 β-carotene β-carotene (Figure F14) is a precursor to vitamin A.Vitamin E is part of a family of compounds called tocopherols. shellfish. peaches and apricots. green peppers. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 Figure F15 Phenol. Naturally occurring antioxidants include vitamin C. CH3 HO CH3 H3C CH3 Figure F13 Vitamin E. They are commonly used as preservatives to extend the shelf life of foodstuffs. vitamin E. CH3 CH3 CH3 H3C H3C CH3 CH3 Figure F14 β-carotene. eggs. Figure F12 Ascorbic acid (vitamin C). OH Synthetic antioxidants Synthetic antioxidants act as free-radical scavengers preventing oxidation via a free radical mechanism. 12 F FOOD CHEMISTRY . CH3 CH3 CH3 Selenium Selenium is found in fish. Smoked salmon and cured meats such as Parma ham and Westphalian ham are examples of foods preserved by this method. This family contains a number of compounds with vitamin E activity. broccoli. red meat. cantaloupe melon. squash. It is broken down by cooking at high temperature and also dissolves in water during boiling. raw cabbage and potatoes. β-carotene and selenium. soya beans and vegetable oils such as canola. It is highly fat-soluble and has a vivid red-orange colour. based around a similar chemical structure to that in Figure F13. seeds. whole grains. containing a methylated phenol group. chicken and garlic. kale cabbage. green-leaf vegetables. broccoli. Vitamin E Vitamin E (Figure F13) is a fat-soluble antioxidant found in wheatgerm. strawberries.

The C–O–CH3 group is called an ether group.4.5-di-tert-butyl-4-hydroxytoluene (BHT) Contains a phenolic ring as well as two tertiary butyl side chains. has a ketone functional group on a side chain HO C O ketone group H H H C C C H H H H OH C CH3 CH3 CH3 tert-butylhydroquinone (TBHQ) contains a phenol group and a tertiary butyl group OH Table F4 Structure of various synthetic antioxidants. Specifically this is an aromatic ether. has an ester functional group on a side chain H H H C O ester group O C C C H H H H OH OH 2. CH3 OH HO OH propyl gallate (PG) contains 3 phenolic OH groups. (CH3)3C–.and 3-tert-butyl-4-hydroxyanisole (BHA): differ by the position of the tertiary butyl group. on the phenolic ring structure.5-trihydroxybutyrophenone (THBP) contains 3 phenolic OH groups. 3-BHA is the more effective antioxidant but commercially a mixture is used. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 13 .Structure ether group Name of antioxidant 2-tert-butyl-4-hydroxyanisole (2-BHA) CH3 C CH3 CH3 tertiary butyl group Arrangement 2. CH3 O OH CH3 O 3-tert-butyl-4-hydroxyanisole (3-BHA) CH3 C OH CH3 H3C H3C C CH3 CH3 OH C CH3 CH3 CH3 3. Toluene is an alternative name for methylbenzene.

It is also the principal precursor in the synthesis of vitamin A. They also tend to be less effective at reducing the rate of oxidation when compared to their synthetic alternatives. decreased risk of heart disease. This is needed to ensure that they are safe for human consumption. Traditional food Beneficial effects green tea turmeric oregano blueberries cranberries reduced cholesterol. degradation of the cell membrane and mutation of the genetic code. reduced rate of cancer cell proliferation antibacterial. In a biological setting. 14 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . leading to inactivation of enzymes. β-carotene can be added to margarine to provide colouring (yellow colour). Public consensus suggests that antioxidants are perceived as being beneficial for healthy living and can be useful in the prevention of disease and ageing. prevention of heart disease O Figure F16 The flavonoid core structure. dark chocolate Table F5 Beneficial effects of foods containing flavonoid compounds. policy and scientific testing that must be in place before synthetic antioxidants can be used in food. Antioxidants found in traditional foods Many traditional foods contain another class of antioxidant. Natural antioxidants add colour and an aftertaste that is not always pleasant to foods. the flavonoids (Figure F16). among many other effects. it is often very difficult to ensure the correct implementation and monitoring of the safe use and labelling of food additives in food. possible anti-Alzheimer’s disease effect possible benefits in preventing heart disease and cancer.Free radicals are chemical species that contain an unpaired electron. anti-inflammatory. lower blood pressure. This causes them to be highly reactive. transferring electrons to the enzymes when required. It acts as a reducing agent in important enzymatic processes. free radicals such as the hydroxyl radical (OH•) and superoxide radical (O2−•) can be generated from the metabolism of oxygen. potential benefits in the treatment of Alzheimer’s disease and cancer antimicrobial action decrease cholesterol levels. The beneficial effects of some of these foods are given in Table F5. There is a significant amount of legislation. lipids and DNA. collagen. Across the globe and especially in developing countries. preventing the damaging effects of these very reactive species. Vitamin C is essential for the synthesis of many hormones and the connective protein. Due to their reactive nature they can cause significant cellular damage by reacting with proteins. Use of antioxidants in food Advantages • • • • Naturally occurring antioxidants have been shown to reduce the risk of heart disease and cancer by acting as free radical scavengers. Disadvantages • • • • O Synthetic antioxidants are generally perceived by the public to be less effective and possibly less safe because they are not naturally occurring. prevent bacterial infections in the urinary tract reduced blood pressure. boosting the immune system.

chlorophyll and heme Describe the factors that affect stability of colour in carotenoids. Thus a compound which absorbs the blue-green wavelengths of light will appear red-orange (Figure F17). then circle the tertiary butyl group and identify any other functional groups present. chlorophyll and heme Discuss the issues associated with the use of synthetic colourants Understand the difference between caramelisation and the Maillard reaction in the browning of food redorange bluegreen blue blueviolet Figure F17 A colour wheel. It does not absorb light in the green CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 15 . anthocyanins. anthocyanins.Test yourself 5 The molecule shown here has been synthesised as a potential antioxidant. A pigment is a naturally occurring colourant found in the cells of plants and animals. H3C O OH OH O H H C C C H H C(CH3)3 F4 Colour A dye is a food-grade. • • • yellow yellowgreen green orangeyellow orange Explain the occurrence of colour in naturally occurring pigments. Copy the molecule. water-soluble colourant. synthetic. Learning objectives • Occurrence of colour Naturally occurring pigments possess colour due to their ability to absorb different wavelengths of visible light and transmit or reflect the portion of the spectrum that has not been absorbed. Chlorophylls have a complex structure containing multiple C=C double bonds that allow the compounds to absorb specific wavelengths of light in the visible spectrum. The transmitted or reflected light is the complementary colour to the light absorbed. red violetred violet Chlorophylls are the green pigments that give most plant leaves their characteristic colour. including the range of colour and sources of carotenoids. Chlorophyll a (Figure F18) absorbs visible light in the blue (400–500 nm) and red (620–700 nm) regions of the visible spectrum.

Chlorophylls therefore appear green as do the leaves in which these compounds are found in high concentrations. Anthocyanins Anthocyanins are the most widely occurring pigments in plants. 16 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . (b) myrtillin found in blackcurrants and blueberries. blueberries. chlorophyll and heme. They all have a characteristic structure based on the same core unit. raspberries and grapes (Figure F19).a b N– Mg2+ O N N– O O O O H Relative absorbance 300 ultraviolet N 400 violet 500 blue 600 green yellow 700 red 800 infrared Wavelength / nm Figure F18 (a) The structure of chlorophyll a. carotenoids. blackcurrants. cranberries. part of the spectrum (500–600 nm) and so these wavelengths of light are transmitted. Anthocyanins are the principal pigments responsible for the pink. (b) its visible light spectrum. Dyes appeared coloured for exactly the same reasons as described above. Naturally occurring pigments Naturally occurring pigments include anthocyanins. strawberries. Foods may have colour due to the presence of naturally occurring pigments or the addition of artificial dyes. blue and purple colours of many fruits and vegetables including red cabbage. a OCH3 OH + O b OH OH + O HO OCH3 O HO HO O OH OH HO OH O HO HO O OH OH OH OH Figure F19 (a) Oenin found in purple grape skin. red.

a a CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 OH b b OH HO HO O O CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 OH OH OH O O OH OH OH OH OH OH HO HO HO HO O HO HO HO HO OH O O O OH OH OH O O O O O O CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 O O O O O O OH OH Figure F21 (a) Lycopene found in tomatoes and watermelons. the astaxanthin becomes dissociated from the protein and the shell turns red. Many of the carotenoids are precursors of vitamin A. sweet peppers and saffron (Figure F21). Astaxanthin is also responsible for the deep pink colour of wild salmon. OH CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 17 . tomatoes. carrots.a H3C CH3 CH3 CH3 OH CH3 b CH3 CH3 CH3 H3C H3C CH3 CH3 CH3 CH3 CH3 Figure F20 (a) Retinol (vitamin A). Carotenoids Carotenoids are the most widespread pigment found in nature. when it is complexed with protein. When the shellfish is cooked. gives live lobsters and crabs their blue-green hue. The structural similarities between vitamin A and β-carotene can be seen in Figure F20. primarily due to their abundance in algae. The red carotenoid astaxanthin (Figure F22). watermelon. (b) β-carotene. Carotenoids generally transmit or reflect longer wavelengths of the visible spectrum (absorb in the blue-violet region) and so have colours in the yellow-orange-red region. (b) crocin found in saffron. Farmed salmon are fed supplements that include astaxanthin so that their flesh matches the colour of wild salmon. Carotenoids are present in bananas.

CH2 N CH N Heme Heme is the red pigment found in the haemoglobin of red blood cells and the myoglobin of muscle tissue (Figure F23). oxidation. At low pH (1–3) the red flavylium form predominates. OH HO OH carbinol HO O+ O OH OH OH pH 1–2 OH OH pH 4–5 quinoidal base (blue) OH HO OH chalcone OH H OO OH O O OH pH 6–7 OH pH > 7 18 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . CH2 H C H3C N– HC N H 3C C H Fe 2+ – CH3 Chlorophylls These are the major pigments in green plants responsible for harvesting light energy – the first stage in the process of photosynthesis. When the pH is increased. Major factors affecting pigment colour are: temperature. Effects on anthocyanins (A) Anthocyanin Structural form (A) (AH ) (B) (C) + (AH+) (B) (C) Colour blue red colourless quinoid flavylium chalcone carbinol base colourless In aqueous solution. the chalcone is formed. The heme in myoglobin is what gives meat its purple-red colour. the blue quinoid (pH 6–7) and colourless carbinol (pH 4–5) forms may be produced. pH. anthocyanins exist in a complex equilibrium between four different structural forms (Table F6). CH3 Stability of pigment colours COOH HOOC Figure F23 The structure of the heme prosthetic group. The position of the equilibrium depends on the pH and temperature of the solution. flavylium cation (red) Table F6 Structural forms and colour of anthocyanins. Numerous factors affect the stability of pigments.O H3C CH3 CH3 CH3 H3C OH HO O CH3 CH3 CH3 H3C CH3 Figure F22 Astaxanthin.Variation in these factors may result in the loss or change of pigment colour. These factors contribute to changes in the structure of the pigment and/or the way in which it absorbs certain wavelengths of light. presence of metal ions and the oxidation state of these metal ions. In basic conditions.

e. the iron ion at the centre of the heme porphyrin ring CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 19 . These metal ions can come from the packaging in canned fruit and often causes discoloration in these food products. the equilibrium shifts to the right causing the pigments to lose their colour. carotenoids are not only coloured but highly susceptible to photo-oxidation and oxidation by metals and organic hydroperoxides (R–O–O–H). the conjugation is destroyed and the pigment is bleached (decolorised). but in an acidic solution (pH 3) it is highly unstable. brighter-green vegetables are viewed as more appealing than darker coloured ones. Heme Freshly cut meat has a purple-red appearance due to the predominance of the pigment myoglobin in the tissue. therefore. When heated above 50 °C.At low temperatures. The magnesium ion located at the centre of the porphin ring (see Figure F18a on page 16) is normally stable and difficult to remove. Generally. to withstand most forms of food processing without being degraded. chlorophyll remains stable. Anthocyanins are able to form vivid. however. NaHCO3) to the water during boiling may also help to keep the vegetables green as this raises the pH. Adding a small amount of sodium hydrogencarbonate (bicarbonate of soda. Carotenoids are thermally stable up to 50 °C and structurally stable in acidic conditions (pH range 2–7). the coloured forms are abundant. If freshly cut meat is exposed to air it changes colour within an hour. but at low pH. which leads to browning of the food. but as the temperature rises. multiple C=C double bond system. A conjugated system is a system of alternating C=C double bonds and C–C single bonds. deep-coloured complexes with Al3+ and Fe3+ ions. the plant cell membranes break down and cause acid to be released. thus decreasing the pH of the surrounding solution. They tend. In both these complexes. Effects on chlorophylls Chlorophylls can be destabilised by high temperatures depending on the pH of the environment. This also causes them to lose their potent antioxidant ability. The oxidised species are also unable to be converted to vitamin A and often have an unpleasant odour. the production of pheophytin and discoloration can be minimised. the Mg2+ ion is displaced by two H+ ions. On oxidation. When oxygen in the air binds to the purple-red myoglobin (Mb) it forms oxymyoglobin (MbO2) which is red – the colour most people associate with meat being fresh. cooked. The heat-induced cellular degradation can also predispose the chlorophyll pigments to photo-degradation in which they chemically decompose in the presence of light. by reducing cooking time and boiling vegetables with the pan lid off to allow the escape of volatile acids. Effects on carotenoids Due to the presence of a conjugated. When plant material is heated. the abundant naturally occurring all-trans form rearranges to yield a variety of cis isomers. i. resulting in formation of an olive-brown pheophytin complex. In an alkaline solution (pH 9).

Another colourant. Over time. Other synthetic dyes with alleged harmful effects include Brilliant Blue (E133) and Erythrosine (E127). some of them extremely serious. the myoglobin and oxymyoglobin undergo auto-oxidation in which Fe2+ is oxidised to Fe3+ which results in the formation of metmyoglobin (MMb) which has an undesirable brownred colour and indicates that the meat is no longer fresh. Since then many problems have been encountered. However. and is used to give glacé cherries their distinctive red colour. Sunset Yellow (E110). It is still legal in the UK. but rather are made of white fish (surimi) containing an artificial flavour and cochineal to make them taste and look like crab meat. A suspected carcinogen banned in one country may be a commonly used additive in another. Due to the international trade in food. So-called ‘crab’ sticks do not actually contain any crab meat. Little was known about the safety of food additive compounds and the associated health implications of their distribution into the populous during their early development. has been banned in the USA for over 30 years as it is suspected by the Food and Drugs Administration (FDA) of being a carcinogen. which prevents oxidation from occurring and the meat from discolouring. to make it more appealing and saleable.(see Figure F23 on page 18) is in the +2 oxidation state (Fe2+). including synthetic colourants. 20 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . Formation of metmyoglobin in meat products can be reduced by packaging the food in low-gas permeability film or hermetically sealing them in oxygen-free conditions. this lack of uniformity is of major concern as imported foods may contain potentially harmful chemicals. Each country may have its own specific set of guidelines and policies for the use of additives in foodstuffs. a code known elsewhere in the world as the International Numbering System (INS). Amaranth (E123). The main problem facing society concerning food colourants is the current lack of uni ed global legislation governing their use. are given ‘E numbers’ in Europe. Non-enzymatic browning There are two principal processes by which non-enzymatic browning of foods occurs: the Maillard reaction and caramelisation. myriad artificial additives have been put in food to make it more flavoursome and colourful – in general. The storage gas used in the packaging of many meat products is 100% CO2. Safety issues associated with dyes and synthetic colourants Food additives. Many of the products you have in your fridge and pantry will not actually contain sources of the food they purport to be. oxidation deoxygenation oxidation oxymyoglobin (MbO2) red myoglobin (Mb) oxygenation metmyoglobin (MMb) reduction purple-red (Fe2+) brown-red (Fe3+) This interconversion between the three forms of myoglobin happens readily. has been linked to severe allergic reactions and also to hyperactivity in children. One commonly used food colourant. if meat is left exposed to air for several days. however. There have been repeated calls for its withdrawal from the marketplace.

as well as by using high temperatures in excess of 120 °C. Cysteine and lysine are amino acids. which occur when baking and roasting foods with a high sugar content. Baked-egg dishes go brown on top as a result of caramelisation. The rate at which the Maillard reaction takes place can be accelerated by increasing the temperature (frying. The brown colour of chocolate does not come from the Maillard reaction as cocoa is naturally brown. The products of decomposition give food its resultant nutty.g. the production of milk chocolate and toast browning. When foods are boiled. Nitrogen-containing compounds must be absent otherwise the Maillard reaction will occur. Milk contains both protein and lactose sugar and so browns by the Maillard reaction. the Maillard reaction is partly responsible for the flavour of milk chocolate. lactose) to yield a mixture of products and water as it is a condensation reaction. Caramelisation Caramelisation is a form of non-enzymatic browning that occurs in foods with a high content of carbohydrates. The Maillard reaction occurs spontaneously at room temperature. caramel-like aroma. The browning effect of the reaction becomes appreciable only at the temperatures involved in cooking. Lysine-containing foods (e. but cysteine-containing foods develop a minimal brown colour. roasting).The Maillard reaction This form of non-enzymatic browning occurs in foods containing both protein and carbohydrate. fudge and toffee by heating sugar (carbohydrate) with cream (protein). caramel is not formed by caramelisation but rather by the Maillard reaction. low moisture levels.g. glucose. The process involves a reaction between the amino group of an amino acid and a reducing sugar (e. However. Examiner’s tip Despite the obvious name. in which a high temperature causes the sugars to oxidise and decompose to form volatile compounds that may then go on to polymerise. Test yourself 6 Use the colour wheel on page 15 to suggest the colour of compounds that absorb the following colours of visible light: a green b orange c red 7 Name two classes of naturally occurring pigments. but the effects of the reaction are not noticeable because the rate is slow. neither caramelisation nor the Maillard reaction occur appreciably as the temperature is not sufficiently high. while the products of polymerisation make the food light-brown. The rate of caramelisation can be increased by catalysis with a base (pH > 9) or an acid (pH < 3). CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 21 .g. milk) brown very nicely. stewing). Many recipes therefore suggest that meat is browned and vegetables such as onions are caramelised to develop flavour and colour before they are cooked using a method requiring a temperature below 100 °C (e. Examples of the Maillard reaction include the formation of brown caramel. a higher content of monosaccharide sugars and increased levels of specific amino acids such as lysine. especially sucrose and reducing sugars. The Maillard reaction produces desirable outcomes such as a beautiful golden-brown colour (though undesirable colours can also be produced) and a change in smell and/or taste to give a caramel or nutty aroma. Caramelisation involves the process of pyrolysis. maltose.

vegetables and rice. So-called ‘Golden Rice’ has been genetically modified by inserting genes from daffodil and a bacterium. quality and shelf life – improves upon currently available foods and makes the GM products more desirable and saleable. 9 Enhanced yield of dairy products – such as milk and eggs. fruits. Caenorhabditis elegans. • • Understand what is meant by a genetically modified organism Discuss the advantages and disadvantages of using genetically modified foods In the transgenic pig. 6 Production of ‘healthy’ crops – which can produce higher levels of useful unsaturated fatty acids and fewer saturated ones. from barren soil efficiently. In the production of transgenic species. Ideal for feeding a growing population or meeting increased consumer demand for a product. the inserted gene designed to make the pig produce more omega-3 oils came from the microscopic nematode worm. The food can be substantially different from or essentially the same as the conventional food. the ability to grow in a hot climate with limited water and mineral availability. GM foods have been available in the marketplace since the 1990s. in terms of composition. pests and herbicides – inserted genes could confer these beneficial characteristics on crops to prevent damage from microbial infection or attack by damaging pests such as beetles and locusts. 4 Improved crop resistance to disease. heavy metals). Benefits of GM foods 1 Increased yield and nutritional content of crops – of particular benefit to developing countries with exploding populations and those prone to famine or endemic malnutrition. The process of genetic modification involves the insertion or deletion of specific genes in the GM organism to produce the desired characteristics. nutrition. 3 Ability of crops to grow in adverse conditions – for example. 7 Improved productivity and feed efficiency in GM animals – means that livestock would require less food per kilogram gain in body mass. It may also be possible to modify crops so that they contain ‘medicinal’ compounds such as antioxidants or anticancer compounds. 22 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . taste. the inserted genes come from a completely unrelated organism and this is partly where the controversy lies.g. Some animal-derived GM foods have been developed including (in 2006) a transgenic pig genetically modified to be rich in ‘good’ omega-3 fatty acids. use of vegetable oils as biofuel – a renewable alternative to gasoline). so that it is enriched with vitamin A. 10 Replacement of chemical insecticides and herbicides – with ‘environmentally friendly’ bioherbicides and bioinsecticides to eradicate damaging weeds and pests. Most GM food is plant-based and includes products such as vegetable oils. smell. Increasing yield also permits diversification in the uses of some crops (e. allowing it to be farmed again. texture and functional characteristics.Learning objectives F5 Genetically modified foods A genetically modified (GM) food is defined as a food derived or produced from a genetically modified organism. 5 Enhanced taste. texture. 8 Improved animal health – GM animals could also be developed to be more resistant to disease.g. It might be possible to grow GM plants that are able to remove pollutants (e. drought. 2 Reduced maturation time for crops – increases annual yield and permits more frequent harvests.

F FOOD CHEMISTRY 23 . This uniformity is described as homogeneity. largely immiscible. Imagine the effects of a disease. gummy. phase (continuous phase). Effects on the environment and human health may take many more years to be apparent. 5 Alteration of the composition of a balanced diet – by changing the nutritional content and quality of foods. in mayonnaise the oil and vinegar are different phases). viscous and rough. 6 Exploitation and monopolisation – by countries and companies with the intellectual property rights to the technology.g. The particles which are finely dispersed make up the dispersed phase. 3 Alleged increase in allergies – especially in those working directly with GM organisms. natural species with unknown effects. Developing countries may become dependent on GM foods.11 Improved conservation of water. general disgust at consuming modified animal products and animal welfare. 4 Damage to the environment and unbalancing of ecosystems – may lead to the endangerment of multiple species and upset the current balance of ecosystems and food chains worldwide. This type of system is called a dispersed system or a colloid. 7 Ethical considerations – include tampering with nature. Many individual foods have the same textural qualities throughout – there is no change of texture within the food. less water and less management. This is because they contain very small particles (too small to be seen with the naked eye) of one phase dispersed in another. crispy.and herbicide-resistant gene becoming fully integrated into several species of pervasive weeds. Some of the arguments against genetic modification include: 1 Not enough is known about the long-term effects – as GM foods are a fairly modern invention. Phases are different substances separated by a boundary (e. A gene conferring antibiotic resistance could possibly be transferred to a species of bacteria making it more difficult to treat infection. There is still much to learn about the way in which genes operate and interact. Imagine smoke rising from a fire – the smoke appears as a uniform and continuous grey blanket. Concerns about GM foods There is significant lobbying and opposition to the use and globalisation of GM foods. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 Learning objectives • • • Understand what is meant by a dispersed system and their relationship to the texture of food Distinguish between emulsions. when it is actually billions of microscopic solid particles floating in air. F6 Texture The texture of foods can be described using many different adjectives including soft. Better natural waste management is an additional benefit. not enough is known about the long-term effects of their introduction. The two phases (solid smoke particles and gaseous air) are immiscible – they remain separate and discrete and yet the overall impression is one of homogeneity (though the solid particles could be seen easily under a microscope). The phase they are dispersed in is called the continuous phase. suspensions and foams in food Describe the action of emulsifiers A dispersed system can be de ned as a kinetically stable mixture of one phase (dispersed phase) within another. 2 Escape of transgenic material into the ‘wild’ – possible contamination of indigenous. Many foods appear homogeneous although they actually contain components that are immiscible with each other. soil and energy – GM crops can be engineered to require less space.

dispersed phase – vinegar). beer froth. salad dressing whipped cream (continuous phase – liquid cream.There are various dispersed systems possible (many are found in foods) depending on the phases involved. Examples are shown in Table F7. Lecithin is used in chocolate bars to help the cocoa solids and butter mix and in mayonnaise to help the oil and vinegar form an emulsion. Surface tension causes liquids to try to have minimum surface area. the rate of coalescence is significantly reduced 24 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . an oil. dispersed phase – air). dispersed phase – cocoa solids). This allows it to bind to both oil and water and to prevent the small droplets of each from separating. Compare a cup of black coffee (solution – see-through) to a cup of white coffee (dispersed system – not see-through). soufflé liquid liquid liquid solid solid liquid gas liquid gas The colloidal particles of the dispersed phase scatter light so you cannot see through a colloid. Egg yolk contains a substance called lecithin. Emulsifiers are added to emulsions and foams to prevent the individual phases from separating from one another and to maintain homogeneity. Emulsifiers act as an interface between the liquid continuous phase and the solid or gas dispersed phase holding them together. Typical emulsifiers used in food production include mustard and egg yolk. Dispersed phase solid Example melted chocolate (continuous phase – molten cocoa butter. mixed or whisked together using mechanical energy. cream. Lecithin contains phospholipid and glycolipid molecules. Generally. thus keeping the two phases bonded together (Figure F24). They aid the formation of emulsions or foams. raw meringue jelly cooked meringue. emulsi ers have both hydrophilic (water-liking) and lipophilic (fat-liking) properties and can therefore dissolve in both the continuous and dispersed phases helping bind them together. To make an emulsion. larger droplet the surface area is less. Mustard contains mucilage which consists of long-chain polysaccharides and polypeptides. This is useful for making vinaigrettes. many natural food colourings mayonnaise (continuous phase – oil. Emulsifiers Emulsifiers are substances that increase the kinetic stability of a dispersed system. therefore it is favourable for the colloid to separate out. Emulsifiers lower the surface tension between two liquids and stabilise the emulsion. This breaks the intermolecular forces between the molecules in each of the phases and causes them to form minute droplets that take some time to coalesce back into large globules. When two droplets collide and combine to form a single. In most foods the continuous phase is a liquid and the state of the dispersed phase varies. Type of dispersed system Continuous phase sol (can also be called a suspension) emulsion foam gel solid foam Table F7 Dispersed systems. water and an emulsifier need to be beaten. These have fatty acid chains which will dissolve in the oily phase of the emulsion (lipophilic) and polar phosphate/sugar heads which will dissolve in the aqueous phase (hydrophilic).

ketones and alcohols. a C–H bond undergoes homolytic ssion to produce two free radicals. This yields a mixture of volatile and unpleasant ‘off ’ smelling compounds including aldehydes. linoleic acid). CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 RH represents any unsaturated fatty acid with hydrogen atoms that can be lost to form free radicals (e. such as pectin or agar. RH → R• + H• The homolytic fission of the C–H bond requires a significant amount of energy input due to the strength of the C–H bond (412 kJ mol−1). and emulsifiers. As with other free-radical chain reactions. The principal mechanism by which auto-oxidation is thought to occur is a free-radical chain reaction. propagation and termination steps.g. in the presence of stabilisers. Test yourself 8 For each of the following dispersed systems (colloids) give the state of the continuous phase and dispersed phase: emulsion foam 9 State what types of dispersed system (colloid) are present in each of the following foods: mayonnaise froth on cappuccino beaten egg white hot chocolate F7 Oxidative rancidity (auto-oxidation) Oxidative rancidity (auto-oxidation) Fats turn rancid spontaneously in the presence of atmospheric oxygen by the process of auto-oxidation. While emulsifiers help the two phases of a dispersed system to form an emulsion. F FOOD CHEMISTRY 25 . HL Learning objectives • • Describe the free radical mechanism of oxidative rancidity in fatty acids Understand the role of lipid peroxides as key intermediates during rancidification Initiation In the first step. The key intermediates in the process are organic hydroperoxides (ROOH). a stabiliser works to prevent the phases from separating.hydrophilic head lipophilic tail OIL emulsifier water molecules Figure F24 Emulsifier structure. the process can be split into initiation.

R1 C + R2 aldehyde O Figure F25 The formation of volatile molecules from the decomposition of a lipid peroxide. or on catalysis with transition metals. Termination In the termination steps. H R1 H O H R1 C O C O UV R2 ultraviolet radiation H R1 C O R2 + OH ketone R2 + R R1 C O H R2 + RH Examiner’s tip The equations for the decomposition reactions of lipid hydroperoxides are not required for the exam. which can subsequently react with oxygen and continue the chain reaction. The decomposition of the hydroperoxide is dependent on photolysis (split by light) of the O–O bond. When the hydroperoxide decomposes. the partial hydrogenation of unsaturated fats uses metals such as nickel as catalysts. but an understanding that decomposition occurs to yield ketones. lipid peroxide Examiner’s tip Remember. so there are trace amounts of these metals in products such as margarine. This stage produces a mixture of compounds. In• + RH → In–H + R• HL Propagation The alkyl radical (R•) produced in the initiation step now reacts with oxygen to form a peroxyl radical (ROO•). This peroxyl radical is able to remove a hydrogen from an intact fatty acid molecule to form a hydroperoxide and regenerate the alkyl radical. aldehydes and other products. it is believed that the removal of a hydrogen atom from the fatty acid chain actually requires an initiator molecule which may be oxygen itself or a free radical present in the substance. R• + O2 → ROO• ROO• + RH → ROOH + R• This mechanism shows how a large number of hydroperoxide molecules can be formed from a small number of free radicals. R• + R• → RR ROO• + R• → ROOR Splitting of the O–O bond requires less energy input than the initial C–H homolysis due to a significantly lower bond enthalpy (O–O 146 kJ mol−1). These new free radicals can react with any of the other free radicals or non-radical species present to produce the aldehydes. Test yourself 10 Draw out a reaction sequence to show how pentan-3-one could be formed from a suitable organic hydroperoxide. 26 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . ROO• + ROO• → ROOR + O2 Further reactions of the organic hydroperoxides The organic hydroperoxides (ROOH) undergo further oxidation and decomposition to produce more free radicals and a wide variety of products. two free radicals combine to form a non-radical species. is expected. as well as additional free radicals. ketones and alcohols responsible for the disagreeable odour of rancid fat (Figure F25).Extension The exact mechanism of initiation in auto-oxidation is poorly understood. Iron is a commonly occurring transition metal in many foods and also promotes rancidification. a hydroxyl radical is also formed.

BHT and TBHQ (see pages 12 and 13) act as free radical scavengers. That is. an antioxidant radical (A•) is produced. Eventually. O CH3 O CH3 CH3 CH3 CH3 Describe the mechanism of action of free radical scavengers Understand the role of chelating agents as antioxidants Explain the function of reducing agents as antioxidants CH3 CH3 CH3 CH3 CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 27 . but these are less reactive than the other free radicals present because of delocalisation of the free electron (Figure F26). In doing so. such as vitamin E (tocopherols). the antioxidant radical is removed in a termination step forming a non-radical species. The antioxidant reacts with free radicals so that they are not available to react with lipid molecules. oxygen or other free radicals. they prevent the formation of free radicals during the initiation step.F8 Antioxidants There are three main types of antioxidants: free-radical scavengers (freeradical quenchers). During initiation: RH → R• + H• AH + R• → RH + A• where AH is the antioxidant molecule. HL Learning objectives • • • Free-radical scavengers (quenchers) Antioxidants (AH). (b) vitamin E radical (A•). or they ‘mop up’ free radicals during the propagation steps of lipid auto-oxidation and thus prevent a chain reaction. During propagation: R• + O2 → ROO• ROO• + AH → ROOH + A• ROOH → RO• + HO• RO• + AH → ROH + A• HO• + AH → H2O + A• a CH3 HO CH3 H3C CH3 b O CH3 H3C CH3 Figure F26 (a) Vitamin E (as AH). BHA. chelating agents and reducing agents.

fish and shellfish. By preventing metal-catalysed oxidation. [EDTA]4−. and preventing discoloration of canned fruits and vegetables by chelating Al3+ and Fe3+ ions. One method of removing ‘active’ metal ions from solution is to use a chelating agent (from the Greek meaning ‘claw’) which essentially wraps the metal ion up inside a molecular cage. O HO C CH2 N CH2 HO O – O O– O– O O C O O C C N H2 H2 O C CH2 CH2 C OH OH Figure F27 Ethylenediaminetetraacetic acid (EDTA) in its uncharged form. like clutching a coin in a closed fist. One well-known and commonly used synthetic chelating agent is ethylenediaminetetraacetic acid or EDTA for short (Figure F27). Chelating agents The decomposition of organic hydroperoxides may occur in the presence of metal ions and so removing these ions from solution acts to reduce the rate of hydroperoxide decomposition and rancidification of fats. [EDTA]4− is effective at: reducing non-enzymatic browning of potato products. with available lone pairs of electrons on the four O− atoms and the two nitrogens. In doing so. literally meaning six teeth. This prevents the metal ion from coming into contact with other species such as organic hydroperoxides and thereby prevents the auto-oxidation reaction. EDTA is called a hexadentate ligand. N N M3+ O– O Figure F28 The [EDTA]4− ion bound to a central metal ion in an octahedral coordination complex. EDTA is added as di. tea and ground mustard. 28 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . Natural chelating agents are found in many plant extracts such as rosemary. These six atoms are able to form an octahedral coordination complex with a central metal ion (Figure F28). preventing oxidation of meat products. TBHQ and tocopherols) all contain a phenolic ring structure which is excellent at sequestering free radicals. The hydrogen on the phenolic –OH group is easily removed. In many food and cosmetics products. BHT. The four acidic protons on EDTA partially dissociate in aqueous solution to produce an ion with a 4− charge. the metal ion is almost entirely enclosed in the structure of the [EDTA]4− ion. preventing flavour changes in milk due to oxidative rancidification.HL During termination: R• + A• → RA RO• + A• → ROA ROO• + A• → ROOA HO• + A• → AOH The antioxidants mentioned here (BHA.or tetrasodium EDTA in which the [EDTA]2−/4− ion is already present.

dehydroascorbic acid. a CHO H C OH CH2OH D-glyceraldehyde Apply the D/L. is converted to the oxidised form. When shown in the Fischer projection (see page 2). When applying the D and L system. page 495 in the Coursebook. Amino acids When applying the D and L system to amino acids. They work by acting as electron and hydrogen donors which causes molecular oxygen to be reduced and hence removed (or at least lowered in concentration) from the environment. dehydroascorbic acid (Figure F29). Ascorbic acid reduces oxygen to water and. it is the chiral carbon furthest away from the carbonyl group that is important. If the molecule is not shown in Fischer projection it must be considered whether the molecule could be converted by a series of chemical reactions into D.3-dihydroxypropanal) is used as a reference. (b) the oxidised form of ascorbic acid. Learning objectives • • • The D and L system The D and L convention for naming enantiomeric forms of a molecule tends to be used for carbohydrates and amino acids. R and NH2 groups around the chiral carbon. the molecule glyceraldehyde (2. in the process. the ‘CORN’ rule is used. HL a HO HO H HO OH O b HO HO H O O O O O F9 Stereochemistry in food Naming enantiomeric stereoisomers Several different systems are employed for naming the enantiomers present in food. HO HOH2C D-glyceraldehyde Figure F30 The reference compound glyceraldehyde in (a) Fischer projection and (b) tetrahedral projection. If it could be converted into D-glyceraldehyde then it is assigned the label D. if the –OH group is on the left. we can compare them to glyceraldehyde to determine which is the D enantiomer and which is the L form (Figure F31). the molecule is given the D notation. The chiral centre is on the central carbon in glyceraldehyde (Figure F30). it is given the L notation.or L-glyceraldehyde. This rule looks at the positions of the COOH. When applying the D and L system. The D and L system is based on the spatial con guration of groups around a chiral carbon atom. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 29 .Reducing agents Antioxidants falling into this class include the carotenoids and ascorbic acid (vitamin C). if the –OH group on this important carbon is on the right. Figure F29 (a) The reduced form of ascorbic acid. Looking at two forms of glucose in the Fischer projection. R/S and (+)/(−) systems for naming enantiomers Discuss the different occurrence of enantiomers in food Distinguish the properties of different enantiomers found in food b CHO HO C H CH2OH L-glyceraldehyde CHO C H H CHO C OH CH2OH L-glyceraldehyde Examiner’s tip Remind yourself about enantiomers by looking at Chapter 10.

These rules give higher priority to atoms attached to the chiral carbon that have a higher atomic number. the molecule is drawn in a tetrahedral projection with the lowest priority group (priority 4) pointing away from the viewer. The groups around each chiral centre are assigned a priority value according to a set of rules called the Cahn–Ingold–Prelog priority rules (CIP). If looking from the COOH to R to NH2 you go in a clockwise direction. anticlockwise therefore L R C clockwise therefore D CH3 CH3 N H2N H L-alanine COOH HOOC mirror plane CO C H D-alanine NH2 H pointing away from you Figure F32 D and L stereoisomers of the amino acid alanine. Latin for ‘on the left’) (Figure F33). If you look at the remaining three groups in priority order (1 → 2 → 3) and you go in a clockwise direction from 1 → 2 → 3. Once the order of priority has been determined. if going from 1 → 2 → 3 you go in an anticlockwise direction. the structure is the D form. The R and S system Using this system we assign the absolute configuration of a chiral centre based on the spatial arrangement of groups. The molecule is drawn in a classic tetrahedral projection with the chiral carbon at the centre and the single hydrogen atom pointing away from the viewer. the enantiomer is the S form (standing for sinister. the enantiomer is the R form (standing for rectus. Latin for ‘straight). 30 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 .HL molecules arranged with CHO at top CHO CHO HO H HO HO H HO H H OH H OH OH CH2OH D-glucose H OH H H CH2OH L-glucose same arrangement of H and OH CHO H C OH CH2OH D-glyceraldehyde CHO HO C H CH2OH L-glyceraldehyde Figure F31 Fischer projections of the two stereoisomers of glucose and their relationship to glyceraldehyde. if you must go anticlockwise it is the L form (Figure F32).

anticlockwise. the enantiomer is the (−) or (l) form. for example. (d) and (l) stand for dextrorotatory (from the Latin dexter meaning ‘right’) and levorotatory (from the Latin laevus meaning ‘left’). D-glyceraldehyde is the (+) form. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 Examiner’s tip Do not confuse the (d) and (l) system with D and L system as they are based on different things. O C OH > O C H H > HO C H decreasing priority The (+) and (−) system These isomers are also known as (d) and (l) forms. when two atoms attached to the central C have the same atomic number. therefore R 2 HL Br C 3 CI F4 I 1 1 I F4 CI 3 lowest priority group pointing away from you S-enantiomer mirror plane lowest priority group pointing away from you R-enantiomer Figure F33 R and S enantiomers of CFClBrI. F FOOD CHEMISTRY 31 . R and S can be assigned from the structure of the molecule obtained using a technique such as X-ray crystallography. but rather the direction in which each enantiomer rotates the plane of polarised light. and in the groups shown here the group on the left has higher priority as the C with O (higher atomic number) is closer to the chiral centre. The labels (d/l) and (+/−) can only be assigned using a polarimeter. H H C H H C H HO C H H H C OH COOH H HO 1 4 2 C 3 clockwise. Priority of other groups With larger groups which have the same atom attached to the central C. In the COOH group the C has an O attached (higher atomic number). we must look at the atoms joined to those atoms. whereas the CH3 only has Hs (lower atomic number) attached. The OH group has the highest priority as O has a higher atomic number than C and H. if the plane of plane polarised light is rotated anticlockwise. > H C H H C H Double bonded atoms count as two groups attached to an atom. If the plane of plane polarised light is rotated clockwise (when viewed with the light approaching the viewer) then the enantiomer is designated (+) or (d). therefore S 2 Br C clockwise. Consider the enantiomer of lactic acid (2-hydroxypropanoic acid) shown in Figure F34. referring to the direction of rotation of the light. The COOH group is assigned a higher priority than CH3 as. thus CHO has higher priority than CH2OH as it is counted as if there are two O atoms attached to the C. Thus –CH2CH3 has a higher priority than –CH3. The three systems do not always match up with each other. but D-alanine is the (−) form. This system is not based on the spatial positioning of the groups around a chiral centre. we keep going along the chain until there is a difference between the groups. therefore R CH3 lowest priority group pointing away from you Figure F34 An enantiomer of lactic acid.

in fact. odours and toxicities. O Figure F37 R(+) and S(−) enantiomers of alpha-ionone. Examiner’s tip The IB syllabus describes the fragrance of S(−)-limonene as that of lemons. Other examples of taste being affected by the enantiomeric form of a molecule present include: 1 R(+)-limonene. thousands of pregnant women were dosed with a mixture of both enantiomers (racemate) and many of them gave birth to children with limb abnormalities. R(+)-limonene S(–)-limonene Figure F36 R(+) and S(−) enantiomers of limonene. while the R(−)-carvone enantiomer tastes of spearmint (Figure F35). 32 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 .HL Stereoisomers in food Knowing about the enantiomeric forms of certain compounds present in the food we eat is extremely important because different optical isomers can possess different tastes. the D forms of amino acids taste sweet. S(−)-limonene. For example. This is due to the way in which the enantiomers interact with taste receptors. A classic example of varying toxicity shown by enantiomeric forms of the same compound is the difference in effect between the R and S isomers of the drug thalidomide. Measuring optical activity could. The difference in smell arises because of the way that protein receptors (olfactory receptors) in our nose detect the molecules. Unfortunately. most naturally occurring carbohydrates are of the D form and taste sweet. which means they have little-to-no taste. therefore. being able to distinguish between two enantiomeric forms of a compound based on smell and taste can be very useful in determining the authenticity of the ingredients and the level of processing to which the food has been subjected. See Figure F37. S(−)-alpha-ionone has less raspberry flavour. Synthetic raspberry flavourings contain a mixture of both enantiomers which is why they never taste quite like the real thing! O 2 R(+)-alpha-ionone gives raspberries their natural flavour. but there is significant evidence in available published literature to support the belief that it does. which is described as having a piney or turpentine-like odour (Figure F36). smell of pine. allow us to distinguish between natural food components and components that have been produced synthetically. Many other synthetic food flavourings contain a racemic mixture of both enantiomers. which smells of oranges. O O R(–) H H S(+) Figure F35 The R(−) and S(+) enantiomers of the fragrant molecule carvone. In food science. but cedar wood overtones. S(+)-carvone tastes of caraways seeds and dill. Conversely. Most naturally occurring amino acids are in the L form. while the S form is implicated in causing severe birth defects. The R form is highly effective in treating morning sickness. where only one enantiomer provides the natural flavour.

12 Classify each of the following amino acids as D or L. Learning objectives • • + O C6 C3 C6 Figure F38 The flavylium ion core structure found in anthocyanin pigments. Some examples are shown in Figure F40. including anthocyanins. Quercetin is a flavonol. a b c CH3 H H2N C CI H HO CH2OH C CH3 H3C OHC OH C CH2CH3 F10 Chemical structure and colour Anthocyanins Anthocyanins are based around a flavonoid/flavylium core structure with a characteristic C6C3C6 skeleton and conjugated double bond system (Figure F38). The ends of the chain may terminate in a cyclic (ring) group which may or may not have oxygen-containing functional groups attached. nor does it have sugar groups attached. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 Examiner’s tip The molecule quercetin is not technically an anthocyanin despite being included on the IB syllabus as an example. chlorophyll and heme Explain why natural pigments are coloured Deduce the solubility rules for carotenoids and anthocyanins Individual anthocyanins differ in: • the number of hydroxyl (–OH) and methoxy (–OCH3) side groups present on the rings • the identity. • Describe the similarities and differences in the structures of natural pigments. It does not contain the positively charged flavylium ion core. carotenoids. a b c HL H COOH C H CH3 H2N CH2OH C COOH H2N H CH2C6H5 C COOH H2N 13 Classify the chiral centre in each of the following as R or S. F FOOD CHEMISTRY 33 . Some examples are shown in Figure F39. Carotenoids Most carotenoids are derived from a 40-carbon polyene (multiple C=C double bonds) chain.Test yourself 11 Draw the structure of the 2-amino acid that does not show optical activity. number and position of attached sugar moieties • the types and number of aliphatic or aromatic acids attached to the sugars.

(b) oenin (one sugar). 34 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . while those containing oxygen atoms are called xanthophylls. (d) Heavenly Blue anthocyanin (from Ipomoea tricolor Mexican Morning Glory) which contains caffeic acid groups (in blue) between the sugar molecules. Those carotenoids that contain solely carbon and hydrogen are called carotenes. (c) antirrhinin (two sugars).a b OH OH HO O OH OH c OCH3 OH HO + O OCH3 O HO HO sugar O OH OH O OH OH + O OH CH3 O OH OH HO OH OH O HO HO O O OH d OH HO O+ O O O CH3 O O O OH O HO O OH OH O OH HO OH OH O OH HO HO OH O OH O O HO OH HO OH O OH O HO O O HO O OH OH O OH HL Figure F39 (a) Quercetin (no sugars).

(b) α-carotene (C40H56) – cyclic groups. It exists in two main forms. They are coloured because they are able to absorb specific wavelengths of light in the visible region of the electromagnetic spectrum and therefore transmit coloured light that is missing one or more parts of the full visible spectrum (the complementary colour to the light absorbed). In both these pigments. (d) lutein (C40H56O2) – xanthophyll with oxygen-containing groups. If only electromagnetic radiation in the ultraviolet (UV) or infrared (IR) region of the spectrum is absorbed. which contains a system of conjugated C=C double bonds. which are shown in Figure F41. planar heterocyclic unit called a porphin ring. Heme acts as a prosthetic group in both myoglobin (the pigment in muscles) and haemoglobin (the pigment in red blood cells). CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 35 . Heterocyclic refers to the presence of a ring structure (cyclic) containing carbon and at least one other element (hetero). (c) retinol/vitamin A (C20H30O) – half a carotene unit with cyclic groups. Heme is a complex between a porphyrin unit and an Fe2+ ion. Colour and conjugation Anthocyanins. a compound will be colourless. whereas haemoglobin exists as a tetramer comprising four globin molecules and four heme units. Myoglobin exists as a monomer. a single heme group is bound in a complex with a single molecule of the protein globin. Figure F23 on page 18) Chlorophylls contain a porphyrin unit complexed to a central Mg2+ ion. carotenoids. typically sulfur or nitrogen in chlorophyll. A porphin ring with side group attached at position 1–8 is called a porphyrin (see structure of heme.a b c OH d H OH HO Figure F40 (a) Lycopene (C40H56) – no cyclic groups. chlorophyll and heme are all pigments – they are all coloured. HL Porphin rings (heme and chlorophyll) The principal structure in both heme and chlorophyll is a complex.

Examiner’s tip Conjugation and chromophores are discussed in detail in Option A. In both (b) chlorophyll a and (c) chlorophyll b.e. only certain parts of the spectrum are absorbed depending on the molecule. pages 38 and 40–41 on the CD-ROM. where previously all carbons in the porphyrin unit were planar and sp2 hybridised. the substituent R group is a methyl (–CH3) in chlorophyll a and an aldehyde (–CHO) in chlorophyll b. Given that the energy required to do so is quantised (i. As the size and arrangement of the π-bonds are different in the various anthocyanins. In the classes of molecule here. An organic molecule will absorb visible light and appear coloured if the conjugated system is su ciently long (usually more than eight conjugated double bonds). HL The part of a molecule that absorbs light and is therefore responsible for the property of colour is called a chromophore. the chromophore is a conjugated system alternating single and double bonds that absorbs energy from photons to promote electrons from a lower energy level to a higher one. The longer the conjugated (delocalised) system of alternating single and double bonds. the longer the wavelength of light absorbed (Figure F42). At position 3. A benzene ring counts as three conjugated bonds. takes discrete values). 36 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . a C=C is missing so that the carbon atoms at positions 7 and 8 are sp3 hybridised and tetrahedral. carotenoids. chlorophyll and heme they all absorb light in slightly different parts of the visible spectrum and so have different colours.a 3 4 b R=CH3 CH3 chlorophyll a c R=CHO H O chlorophyll b N 2 5 – N N Mg O 6 2+ N N – N Mg2+ N– O O N – NH 1 HN N O O O N O double bond missing O O O H 8 7 double bond porphin structure H C20H39 Figure F41 (a) The ring structure of a porphin unit.

a H3C CH3 CH3 CH3 15 Would you expect the molecules shown in Question 14 to be water soluble or fat soluble? O CH3 b H3C CH3 H3C CH3 O CH3 H3C CH3 CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 37 . Carotenoids are fat soluble. hydrocarbons and other non-polar molecules.5-triene. The forces between fat molecules are mainly van der Waals’ forces. They contain no/few –OH groups so cannot form any/many hydrogen bonds to water molecules.5-triene has a conjugated system of three double bonds.3.3. Carotenoids are able to form significant van der Waals’ forces with fatty acids.7-triene – the double bonds are not conjugated and this will absorb a shorter wavelength of light than octa-1. Solubility Anthocyanins are water-soluble because they contain numerous hydroxyl (–OH) groups which can hydrogen bond with water molecules. Many of them possess an overall positive charge in the flavylium ring structure permitting electrostatic forces to form between the molecule and water.4. (b) octa-1. Anthocyanins are not fat-soluble due to the extensive hydrogen bonding between molecules due to the –OH groups. The primary type of intermolecular force is van der Waals’ forces as most of the molecule is non-polar. HL Test yourself 14 Explain which of the molecules shown here will absorb longer wavelength electromagnetic radiation. Carotenoids are not water soluble because most of the molecule consists of a non-polar hydrocarbon chain.a H C H H C C H H C C H H C H C H CH3 b H C H H C H C H H C C H H C H C H H C H Figure 42 (a) Octa-1.

This process is called rancidification and is a form of oxidation. Shelf life is an important concept in the selling and marketing of foods. Butter tends to be produced from saturated animal fats while margarine is manufactured from unsaturated vegetable oils. textures and appealing colours in the foods they buy. which fatty acid is most likely to be present in each of the oils. C18H34O2. eicosapentaenoic acid is a poly-unsaturated fatty acid containing five C=C double bonds. This date is an indication of the shelf life of the product. Vaccenic acid. ii State which isomer is more harmful and give two possible reasons for your choice. The composition of foods can be broken down into a number of discrete nutrient groups each with a different chemistry and all need to be represented in a balanced diet. Fatty foods have a shelf life generally determined by the rate at which the lipids decompose to form off-smelling byproducts.Exam-style questions 1 The study of the chemistry of food is an essential part of ensuring food quality and providing consumers with better flavours. [1] [3] [3] [4] [3] [3] [1] [1] [1] [2] Margarine and butter are two similar products used in cooking that differ chemically. during which they react with oxygen to form a number of unpleasant smelling and tasting breakdown products. b Quantitatively describe the effects of three named factors on the shelf life of a food. d Suggest two reasons why it is beneficial to partially hydrogenate the unsaturated fatty acids during the production of margarine. For one of these factors. in terms of structure and bonding. Lipids are prone to rancidification. smells. a State and explain. explain the effect described. Olive oil has a melting point around 0 °C while that of fish oil is < −5 °C. in terms of structure and bonding. It exists as both trans and cis stereoisomers. [1] [1] [2] [4] 38 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . the relative melting points of the two isomers. [2] 3 We are all familiar with the ‘best before’ dates seen on food products at the supermarket. a State two properties of a food that might be adversely affected when it exceeds its shelf life. b i State and explain. is a naturally occurring mono-unsaturated fatty acid found in dairy products. a Describe what is meant by a food. One of the stereoisomers of vaccenic acid is believed to be more harmful to human health than the other. b Give details on the structure and chemical composition of: i a named amino acid ii a named monosaccharide c In which nutrient groups could the following features be found: i a peptide bond ii a glycosidic bond iii an ester linkage 2 Oleic acid is a mono-unsaturated fatty acid. c i By what sort of mechanism do fats undergo rancidification? ii Name a functional group present in the products of rancidification. c i Place the following fatty acids in order (fastest rst) of the rate at which they undergo auto-oxidation: stearic acid oleic acid linoleic acid [1] ii Give one reason for your choice.

synthetic antioxidants are added to perishable items to extend their shelf life. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 [2] [4] [2] [1] [1] [1] [2] [4] F FOOD CHEMISTRY 39 . a Explain what is meant by a dispersed system. [2] iii State and explain two ways in which traditional preservation techniques increase the shelf life of food. c Explain how structure and bonding make lecithin useful as an emulsifier. ii For a named synthetic antioxidant.The shelf life of products can be increased by a number of methods. iii How might the rate of the Maillard reaction be increased? [3] [2] [1] 5 In a world with a rapidly increasingly population. but shake it with an emulsifying agent to prevent the separation process and a vinaigrette is produced. [2] [4] [1] [3] [2] [3] To make bland foods appear more nutritious and tasty. ii Name one food in which the Maillard reaction predominates and one in which caramelisation is the predominant process of browning. Genetic modification of plants and animals is one possible partial solution to this potential disaster. [4] 4 Coloration in foods is due to the presence of naturally occurring pigments within the substance. food and fuel production struggle to keep up. i Name one factor that affects the colour of a pigment. explain how its chemical structure gives it antioxidant properties. ii Describe and explain the effect of varying this factor on the colour of an anthocyanin. One function of colour in foods is to make them more appealing to consumers. There is a significant amount of chemistry behind these processes. d i Describe the main ways in which these two processes are different. synthetic colourants are added by manufacturers. odour and colour. d i Explain how film packaging helps to increase the shelf life of food. the texture of a food is an extremely important factor to humans in determining the ‘likeability’ of a product. The texture and appearance of some foods can be manipulated by the addition of substances with special properties. The texture of a food depends to a large extent on the phases of matter that exist within a food. state which type of dispersed system is present: i melted chocolate ii whipped cream iii jelly iv Name a further type of dispersed system found in foods not included in parts i–iii and describe the phases present. The Maillard reaction and caramelisation are two mechanisms by which foods develop flavours and a brown coloration. There are a number of naturally occurring antioxidants but. c Suggest two problems associated with the worldwide use of synthetic food colourants. There is a very real danger that many countries will simply become unable to feed their people. b Give two arguments for and two arguments against the global use of genetically modified organisms in the food industry. The rate at which food becomes unsafe to eat can be reduced by combining foods with additives such as antioxidants. b For each of the following foods. A separated mixture of oil and vinegar would be unpalatable to most. a Describe the principles behind genetic modification of an organism. ii Name two naturally occurring pigments and give one source for each. 6 Besides flavour. increasingly. including animals in the natural world. a b i Explain why pigments and dyes are coloured.

2-benzoquinone i What name is given to the type of reaction which converts catechol to 1.2-benzoquinone which is red. There are several different naming conventions for distinguishing the enantiomers of a molecule. They are able to slow down the natural process of oxidation. [4] 40 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . This process occurs as the colourless molecule catechol (1.7 During rancidification of fat-containing foods. One type of isomerism is called stereoisomerism. flavour. 8 Antioxidants. ethylenediaminetetraacetic acid (EDTA) needs to exist as a hexadentate ligand. the process of fatty acid auto-oxidation. ii Why are hydroperoxide molecules prone to photolysis? [1] [2] [5] [1] [1] [2] b Describe. odour and colour. a Explain. a i Draw the structure of a hydroperoxide. OH OH O O catechol 1. use R to represent the side group. or isomers. The D and L system for naming enantiomers of amino acids can be applied by using the CORN rule. [1] [1] [3] [1] b Explain how the CORN rule can be used to determine whether an amino acid is the D or L stereoisomer. The key intermediate in the auto-oxidation of fatty acids is an organic hydroperoxide. b i State what is meant by a hexadentate ligand and the shape of the EDTA–metal ion coordination complex. synthetic and natural. using equations. how some antioxidants are able to prevent the auto-oxidation of fatty acids.2-benzoquinone? ii Suggest a chemical species which might bring about this conversion when fruit is either exposed to air or stored in water. fatty acids molecules undergo oxidation. are important in maintaining the chemical environment in which other molecules exist. why might EDTA be expected to lose antioxidant potency in solutions with a very low pH? iii Why is the EDTA useful in preventing the discoloration of canned fruit. such as peaches? [4] [2] [3] [2] c Many fruits go brown when their flesh is exposed to air or when they are chopped and stored in water. To be an effective antioxidant. during which foods undergo changes in texture. a Name the compound used as the basis for the D and L system for naming stereoisomers. ii By considering the answer to part i.2-dihydroxybenzene) is converted to 1. Include the correct terminology for each step. including appropriate equations. c Write equations for the decomposition of an organic hydroperoxyl radical into: i an aldehyde ii a ketone d Suggest two reasons why margarine might undergo rancidification more rapidly than butter. iii Why does adding lemon juice to the water used to store cut fruit reduce the rate at which it goes brown? 9 Compounds with identical chemical formulae may exist in various different forms.

tomatoes and the shell of some shellfish. members of which are found in carrots. They appear close in colour to the naked eye but. Another type of naturally occurring pigment is the carotenoid family. b Identify the subcategory of carotenoid to which each of the following molecules belongs: i [1] [3] ii O O HO OH [1] iii Give a reason for your choices. [3] [1] [3] [2] h Suggest why manufacturers of menthol have spent significant time and money in developing a synthetic route that yields the (−) enantiomer and not a mixture of the (−) and (+) enantiomers. g Suggest one property shared by both (+) and (−) enantiomers of a compound. Most naturally occurring menthol is (−)-menthol. with an absorption maximum of around 520 nm. [2] 10 The absorption spectra of the anthocyanins oenin and antirrhinin are very similar.c Determine whether the following compounds are D or L enantiomers: i alanine ii galactose iii fructose CHO H H H2N O alanine CH3 OH HO HO H C C C C OH H H OH HO H H CH2OH C O H OH OH [3] CH2OH galactose CH2OH fructose d Describe the taste of each of the specific compounds shown in part c. f Explain why it is possible to have pairs of enantiomers designated as S(−) and R(+) as well as S(+) and R(−). and two reasons for the small difference in the wavelength of the maximal absorption. Menthol exists as a pair of enantiomers. under close inspection. a By comparing the structures of oenin and antirrhinin. e Use the R and S system to determine which enantiomer of the amino acid alanine is shown in part ci. [1] CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 F FOOD CHEMISTRY 41 . there is a small variation of a few nanometres in their absorption maxima. suggest one reason they appear the same colour. and one property that might differ.

ii In terms of structure and bonding. iii State and explain whether the naturally occurring molecule betanin could be used as a food colouring. O HO H N O OH [3] [2] [2] O N HO O + O– HO HO O OH OH betanin 42 F FOOD CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 .The structure and bonding present in a molecule is an important factor in determining whether a molecule will be coloured or not. explain why the solvent used in part ci is hexane rather than water. c i Describe and explain what would be expected to happen to the position of the absorption peak for lycopene located in the visible region of the light spectrum. when bromine water is added to a solution of lycopene in hexane.

Sign up to vote on this title
UsefulNot useful