Internationally Accredited Study Program by IFT and IUFoST

ITP 510
Kimia Komponen Pangan

Program Studi Ilmu Pangan

Departemen Ilmu dan Teknologi Pangan, FATETA-IPB
Bahan Tambahan Pangan
Definition
Food additives:
Any substances the intended use of which
results, or may reasonably be expected to
result, directly or indirectly in its becoming a
component or otherwise affecting the
characteristics of any food
if such a substance is not generally
recognized, among experts qualified by
scientific training and experience to
evaluate its safety, as having been
adequately shown through scientific
procedures to be safe under the condition of
its intended use except that such a does not
include pesticides, color additives and
substances for which prior sanction or
approval was granted.
Reasons why food additive is added
❖ Maintain or Improve Safety and Freshness:
▪ Preservatives slow product spoilage caused by mold, air,
bacteria, fungi or yeast. In addition to maintaining the
quality of the food, they help control contamination that
can cause foodborne illness, including life-threatening
botulism.
▪ One group of preservatives -- antioxidants -- prevents fats
and oils and the foods containing them from becoming
rancid or developing an off-flavor. They also prevent cut
fresh fruits such as apples from turning brown when
exposed to air.
❖To Improve or Maintain Nutritional Value
▪ Vitamins and minerals (and fiber) are added to
many foods to make up for those lacking in a
person's diet or lost in processing, or to enhance
the nutritional quality of a food. Such fortification
and enrichment has helped reduce malnutrition
worldwide. All products containing added
nutrients must be appropriately labeled.
❖Improve Taste, Texture and Appearance:
▪ Spices, natural and artificial flavors, and
sweeteners are added to enhance the taste of
food. Food colors maintain or improve
appearance. Emulsifiers, stabilizers and thickeners
give foods the texture and consistency consumers
expect. Leavening agents allow baked goods to
rise during baking. Some additives help control
the acidity and alkalinity of foods, while other
ingredients help maintain the taste and appeal of
foods with reduced fat content.
Types of Food Additives
1. Complex substances such as proteins or starches
that are extracted from other foods (for
example, the use of caseinate in sausages and
prepared meats)
2. Naturally occurring, well-defined chemical
compounds, e.g. salts, phosphates, acetic acid,
ascorbic acid
3. Substances produced by synthesis, which may or
may not occur in nature, e.g. coal tar dyes,
synthetic β-carotene, antioxidants,
preservatives & emulsifiers
PRESERVATIVES
 Benzoic Acid
• Occurs naturally in many types of
berries, plums, prunes & some spices
• As an additive, it is used as benzoic acid
or as benzoate
• Benzoate is used more often because
benzoic acid is sparsely soluble in water
(0.27% at 18oC). Sodium benzoate is
more soluble (66.0g/100 mL at 20oC)
• The undissociated form of benzoic acid is
the most effective antimicrobial agent
• pKa 4.2, pH 2.5-4.0
• Application: high-acid foods, fruit drinks,
cider, carbonated beverages, pickles,
margarines, salad dressings, soy sauce,
jams
 Parabens
• Alkyl esters of p-hydroxybenzoic
acid
• Alkyl groups: methyl, ethyl,
propyl, butyl, heptyl
• Colorless, tasteless, odorless
(except the methyl paraben)
• Nonvolatile, nonhygroscopic
• The solubility in water depends on the nature of
the alkyl group → the longer the alkyl chain length,
the lower the solubility
• Have antimicrobial activity in both acid and alkaline
pH regions
Parabens (Cont’d)
❖The antimicrobial activity of parabens is
proportional to the chain length of the alkyl
group
❖More active against molds and yeasts than
against bacteria (more active against Gram+ than
Gram- bacteria)
❖Application:
▪ fruit cakes, pastries, fruit fillings
▪ Methyl & propyl parabens: soft drinks
▪ Combination of several parabens: fish
products, flavor extracts, salad dressings
 Sorbic Acid
Sorbic Acid • A straight-chain, trans-trans
unsaturated fatty acid, 2,4-
hexadienoic acid
• Low solubility (0.15g/100 mL) in
water, room temperature

• Sorbate: stable in the dry form; unstable in aqueous solutions

(decompose through oxidation)
• pH↓, temperature↑, light exposure: oxidation rate↑
• Effective against yeasts & molds (sorbic acid & sorbates)
Sorbate
• Inhibit yeast growth in a variety of foods
(wine, fruit juice, dried fruit, cottage
cheese, meat, fish products)
• Most effective in products of low pH
(salad dressings, tomato products,
carbonated beverages)
• Effective level in foods: 0.5-0.30%
• Generally used in sweetened wines or wines that contain residual
sugars to prevent refermentation → it does not affect food flavor
• Can be degraded by certain microorganisms to produce off-
flavors
• Molds can metabolize sorbate to produce 1,3-pentadiene (a
volatile compound with an odor like kerosene)
• High level of m.o. can result in the degradation of sorbate in wine
→ results in the off-flavor known as “Geradium off-odor”
• Responsible compounds for the flavor defect: ethyl sorbate, 4-
hexenoic acid, 1-ethoxy-hexa-2,4-diene, and 2-ethoxyhexa-3,5-
diene
 Sulfites
• Sulfur dioxide & sulfites as antimicrobial
substance and antioxidant
• Sulfur dioxide:
▪ Gas that can be used in compressed form in
cylinders

− Liquid under pressure of 3.4 atm

− Can be injected directly in liquids
− Can also be used to prepare
solutions in ice cold water
− It dissolves to form sulfurous acid
 Sulfites
• Sulfurous acid inhibits molds & bacteria to a lesser
extent yeasts
• SO2 can be used to control undesirable bacteria and
wild yeast in fermentations without affecting the SO2-
tolerant cultured yeasts
• The amount of SO2 added to foods:
₋ 200-500 ppm: develop unpleasant off-flavor
₋ ADI: 1.5 mg/kg body weight
₋ Is not permitted in foods that contain significant quantities of
thiamine (it is destroyed by SO2)
• Application: wine, meat products, dried vegetables,
dried potato products
 Nitrates and Nitrites
• Curing salts (e.g. of bacon and ham) have
traditionally contained nitrate and nitrite
• Antimicrobial action
• Nitrate: used in the production of Gouda
cheese to prevent gas formation by butyric
acid-forming bacteria
• Nitrite: involves in the inhibition of toxin
formation by C. botulinum
• Major concern about the use of nitrite: the secondary
amines in foods may react to form nitrosamines
R1-NH-R + HNO2 →R1-N-N=O + H2O
R
 Nitrosamines
• Powerful carcinogens, may be
mutagenic and teratogenic as
well
• Very small amounts of
nitrosamines can be formed in
certain cured meat products
(in ppm or ppb)
• May be either volatile or non-
volatile

• Usually present in foods as the result of processing methods that

promote their formation
• ADI of nitrite: 60 mg/day
 Hydrogen Peroxide
• A strong oxidizing agent
• Also used as a bleaching agent
• Antimicrobial action in the preservation
of cheese and milk
• Decomposes slowly into water and oxygen;
the process is accelerated by increased
temperature and the presence of catalysts
(catalase, lacto-peroxidase, and heavy
metals)
• Its microbial action increases with
temperature
• Can be used for sterilizing food processing
equipment and for sterilizing packaging
material used in aseptic food packaging
systems
Sodium Chloride
• Have been used for centuries to prevent spoilage of
foods
• It is mainly used in combination with other processing
methods
• The antimicrobial activity is related to its ability to
reduce the water activity (aw) → influencing microbial
growth
• Characters:
▪ Produces an osmotic effect
▪ Limits oxygen solubility
▪ Changes pH
▪ Sodium and chloride ions are toxic
▪ Salt contributes to loss of magnesium ions
 Bacteriocins
• Nisin is an antibacterial polypeptide
produced by some strains of
Lactococcus lactis. Nisin-like substances
are widely produced by LAB
• These inhibitory substances are known
as bacteriocins
• Nisin: has been called an antibiotic, but
the term is avoided
• Nisin-producing organisms occur
naturally in milk
• Nisin can be used as a processing aid
against gram-positive organisms
 Nisin (Cont’d)
• Nisin is a polypeptide with a molecular weight of
3500 (dimer of MW 7000)
• Content: some unusual sulfur-AA, lanthionine
and β-methyl lanthionine
• Contains no aromatic AA
• Stable to heat
• Application: processed cheese, the heat
treatment of nonacid foods and in extending the
shelf life of sterilized milk
• Related antibacterial substance: natamycin,
identical to pimaricin
• Natamycin is effective in controlling the growth
of fungi, but no effects on bacteria or viruses
NISIN
 Acids

Phosporic acid

• Dual purposes as FA: as acidulants and as preservatives

• Phosphoric acid (in cola soft drinks to reduce pH)
• Acetic acid: to provide tartness in mayonnaise and salad
dressings
• Similar function by citric, tartaric, malic, lactic, succinic,
adipic, fumaric acid
 Acids (Cont’d)

• Members of the straight-chain carboxylic acids,

propionic & sorbic acids, are used for their
antimicrobial properties
• Propionic acid is mainly used
for its antifungal properties
• The fungistatic effect is higher
at pH 4 than pH 5
• The sodium salts of propionic Sorbic acid

acid also have antimicrobial

properties
ANTIOXIDANT
Antioxidants
• All of the substances that have some effect on
preventing or retarding oxidative deterioration in
food
• Primary antioxidants terminate free radical
chains and function as electron donors
• Phenolic antioxidants, butylated hydroxyanisole
(BHA), butylated hydroxytoluene (BHT), tertiary
butyl hydroquinone (TBHQ), alkylgalates,
propylgallate (PG), natural & synthetic
tocopherols and tocotrienols
• Oxygen scavengers can remove O2 in a closed
system: vit. C & related substances, ascorbyl
palmitate, erythorbic acid
Antioxidants
• Chelating agent or sequestrants remove metallic
ions (Cu, Fe are powerful prooxidants) : citric
acid, amino acids, EDTA
• Enzymatic antioxidants remove dissolved or
head space oxygen (e.g. glucose oxidase):
superoxide dismutase
• Natural antioxidants: spices, herbs; e.g.
rosemary (carnosic acid and carnosol), sage
• Sometimes the antioxidants are incorporated in
the packaging materials rather than in the food
itself
• No more than 50 ppm of the antioxidants
become a component of the food
EMULSIFIER
 Emulsifiers
• Except lecithin, all emulsifiers in foods
are synthetic; derivative of fatty acids
Characteristic:
• Ionic or nonionic
• Hydrophile/ lipophile
balance (HLB)
 Emulsifiers
▪ Hydrophillic-Lipophillic Balance (HLB) : This is a
concept for choosing emulsifiers. The value of HLB
ranges from 1-20.
▪ Low HLB emulsifiers are soluble in oil while high
HLB emulsifiers are soluble in water.
▪ Bancroft's rule tells us that the type of emulsion
(i.e. oil in water or water in oil) is dictated by the
emulsifier and that the emulsifier should be soluble
in the continuous phase.
▪ Low HLB emulsifier's are soluble in oil and give rise
to water in oil emulsions.
Emulsifiers – HLB level

Solubility HLB Range

No dispersability in water 1-4

Poor Dispersion in water 3-6

Milky appearance 6-8

Stable milky appearance 8-10

Translucent to clear dispersion 10-13

Clear solution 13+

HLB values of some food emulsifiers
EMULSIFIER HLB VALUE
Oleic acid 1.0
Acetylated monoglycerides 1.5
Sorbitan trioleate 1.8
Glycerol dioleate 1.8
Sorbitan tristearate 2.1
Propylene glycol monostearate 3.4
Glycerol Monoleate 3.4
Glycerol monostearate 3.8
Acetylated monoglycerides (stearate) 3.8
Sorbitan monooleate 4.3
Propylene glycol monolaurate 4.5
Sorbitan monostearate 4.7
Calcium stearoxyl-2-lactylate 5.1
Glycerol monolaurate 5.2
Sorbitan monopalmitate 6.7
 HLB values of some food emulsifiers
EMULSIFIER HLB VALUE
Sorbitan monopalmitate 6.7

Soy lecithin 8.0

Diacetylated tartaric acid esters of monoglycerides 8.0
Sodium Stearoyl lactylate 8.3
Sorbitan monolaurate ) 8.6
Polyoxyethylene (20) sorbitan tristearate 10.5
Polyoxyethylene (20) sorbitan trioleate 11.0
Polyoxyethylene (20) sorbitan monostearate 14.9
Sucrose monolaurate 15.0
Polyoxyethylene (20) sorbitan monooleate 15.0
Polyoxyethylene (20) sorbitan monopalmitate 15.6
 Lecithin
• Lecithin is the commercial name of
a mixture of phospholipids
obtained as a by product of the
refining of soybean oil
• Phosphatidylcholine ~ lecithin
• Crude soybean lecithin: dark,
bleached with H2O2 or benzoyl
peroxide
• Hydroxylated lecithin: by
treatment with H2O2 and lactic or
acetic acid
• More hydrophilic; makes it a better o/w emulsifier
Lecithin
 HYDROXYLATION OF RAPESEED LECHITIN

LES (Lechitin ethanol soluble fraction)

(Suitable for use in pharmacy
and cosmetics)
 Monoglycerides (MG)

• Produced by trans-esterification of glycerol

with TG; high temperature, under vacuum, in
the presence of alkaline catalyst
• Commercial MG: a mixture about 40% MG & di-
(DG) and triglycerides (TG)
• The emulsifying properties (HLB) are
determined by the chain length & unsaturation
of the fatty acid chain
Hydroxycarboxylic and Fatty Acid Esters
• Produced by esterifying organic acids
to monoglycerides, increasing their
hydrophilic properties
• Acetic, citric, fumaric, lactic, succinic, or
tartaric acid
FLAVOUR
 Flavors
• Including a wide variety of spices, oleoresins,
essential oils, & natural extractives

• A variety of synthetic
flavors contain mostly
the same chemicals
as those found in the
natural flavors; the
natural flavors are
usually more complex
in composition
 Categories of Flavor Compounds
1. Natural flavor & flavoring substances
preparations or single substances obtained
exclusively by physical process from raw
material in their natural state or processed
for human consumption
2. Nature-identical flavors
produced by chemical synthesis or from
aromatic raw materials. They are chemically
identical to natural products used for
human consumption
3. Artificial flavors
substances that are not
present in natural products
Flavour compounds
▪ The first two categories require consideration less regulatory
control than the 3rd one
▪ Application: soft drinks, beverages, baked goods,
confectionary products, ice cream, desserts, etc
▪ Small amounts in food, generally not >300 ppm
▪ Spices and oleoresins: used extensively in sausages and
prepared meat
▪ In recent years, the proportion of natural flavors has greatly
increase
▪ Numerous flavoring substances are on the GRAS list
▪ Significant recent development in the flavor industry: the
production of flavor ingredients using biotechnology
 Flavor Enhancers

• Substances that carry the property of ‘umami’ and

comprise glutamates and nucleotides

• Glutamic acid
− Amino acid (AA)
− Free glutamic acid
• High levels of free glutamate in
many vegetables (mushrooms,
peas, tomatoes)

• Glutamate is an element of the natural ripening

process that results in fullness of taste
Monosodium glutamate
MSG's effect works best in the pH range of 3.5 to 7.2
(mostly "acidic"), which also is the range that most
foods possess.
MSG is useful for intensifying the flavor of high-protein
foods such as meat, fish, eggs, and cheese.
It doesn't work with fruits, fruit juices, sweet spicy
foods, or any other foods rich in sugar and
carbohydrates
 Monosodium glutamate (MSG)
• Similar taste properties in the L-forms of α-amino dicarboxylates with four to
seven carbon atoms
• The intensity of flavor is related to the chemical structure of these
compounds
• Other AA with similar taste properties: salts of ibotenic acid, tricholomic acid,
L-theanine
• Tricholomic acid: isolated from fungi Tricholoma muscarium
• Ibotenic acic : isolated from Amanita strobiliformis
(both are under investigation, probably toxic)
Nucleotides
Nucleotides
▪ Nucleotides are usually used in the form of sodium
salts
▪ disodium guanylate (DSG)
▪ disodium inosinate (DSI)
▪ disodium xanthylate (DSX).
▪ Ribonucleotides : derived from muscle and yeast
RNA by acid hydrolysis, then neutralized with NaOH
▪ Have essentially the same flavor enhancing property
as MSG but are ten times as powerful
▪ More effective when mixed with MSG.
 Nucleotides

Disodium xanthylate (XMP) Disodium 5`-inosinate (IMP): in

meat, poultry, and fish

Disodium 5`-guanylate (GMP): in Adenosine monophosphate (AMP): in

mushrooms (shiitake mushrooms) vegetables, crustaceans, mollusks
 MSG
• Nucleotides w/ ester group (2` or 3` position) → tasteless
• Taste activity will be lost if the ester group is removed by the
action of the phosphomonoesterases
• Important to inactivate such enzymes in foods before adding 5`-
nucleotide flavor enhancers
• Taste intensity of MSG ~ concentration
• Threshold:
− MSG: 0.012 g/100 mL
− NaCl: 0.0037 g/100 mL
− Sucrose: 0.086 g/100 mL
• Strong synergistic effect between MSG & IMP: taste intensity 16x
stronger than the same amount of MSG
• Using flavor enhancers in a food → possible to reduce the salt
level without effecting the palatability/ food acceptance
SWEETENERS
 Sweeteners
Two groups:
1 Non-nutritive sweeteners
saccharin, cyclamate,
aspartame, acesulfame K, sucralose
2 Nutritive sweeteners
sucrose, glucose, fructose, invert
sugar, a variety of polyols including
sorbitol, mannitol, maltitol, lactitol,
xylitol, hydrogenated glucose syrup
 Non-nutritive sweeteners
▪ Cyclamates:
₋ the sodium or calcium salts of cyclohexane sulfamic acid or the acid itself
₋ 30-40 times sweeter than sucrose, 300 times sweeter than saccharin. The
cheapest, heat stable
₋ Approved for use in foods in USA in 1950, now is prohibited
₋ 1967: cyclamate can be converted by intestinal flora in certain individuals
into cyclohexamine, a carcinogen. Some population are nonconverters,
some convert only small amount, some convert large amount

• At higher concentrations, the sweetness intensity of the synthetic sweeteners

increases at a lower rate than that which occurs with sugars. It is ascribed to
the bitterness and strong aftertaste that appears at these relatively high
concentrations.
▪ Saccharine: available as the sodium/ calcium salt of
orthobenzosulfimide
▪ 300 – 400X sweeter than sucrose
▪ has a bitter or metallic aftertaste, especially at high
concentrations

Methyl anthranilate

Maumee synthesis of saccharin.

 Aspartame
• A dipeptide derivative → L-aspartyl-L-phenylalanine
methyl ester
• Approved in USA (1981) for use as a tabletop
sweetener, in dry beverage mixes, in foods that are not
heat processed
• It is metabolized in the body to form
phenylalanine, aspartic acid, and
methanol
• No harmful effects from aspartame
have been demonstrated
• The main limiting factor in the use of
aspartame is its lack of heat stability
 Acesulfame K
• The potassium salt of 6-methyl-1,2,3-oxathiozine-4(3H)-one-2,2-
dioxide
• A crystalline powder, 200 times sweeter than sugar
• The sweetening power depends to a certain degree on the
acidity of the food it is used in
• More stable than other sweeteners
• Clean sweet taste, does not linger
• Kraft Foods patented the use of sodium ferulate to mask
acesulfame's aftertaste
• Approved in 1988
PHOSPHATES
 Phosphates
• Widely used in the form of:
− Phosphoric acid-acidulant
− Monophosphatess
− Polyphosphates
• As buffering agents in dairy, meat, fish
products; anticaking agents in salts; firming
agents in fruits and vegetables; yeast food in
bakery and alcoholic beverages; melting salts
in cheese processing
• Phosphorous oxychloride (POCl3) as a
starch-modifying agent
 Tricalcium phosphate
▪ Calcium salt of phosphoric acid
▪ Its primary function in fortification is to increase the calcium
content of foods.
▪ Plain taste
▪ Almost insoluble in water, chalky texture → free flowing
agent, clouding agent
▪ Adds smoothness and opacity to reduced fat foods and
beverages, such as soymilk
▪ Firming agent – interacts with gelling agents to strengthen a
food structure
▪ Leavening agent in some baked goods & breadings
Sodium tripolyphosphate (STPP) and sodium hexametaphosphate (SHMP)

▪ Used as additive in poultry products

▪ Increasing the temperature required for denaturation of
protein → reduces cook-cool loss, leading to an end product
with greater succulence (juicy)
▪ STPP and NaCl increase ionic strength and synergistically
extract myofibrillar protein. As protein becomes soluble, it
develops a tackiness.
▪ STPP inhibits the oxidative effect of NaCl, and flavor is
maintained. The dark meat of poultry inherently contains
more iron, which can lead to the development of a warmed-
over flavor. Phosphates in a poultry formulation will inhibit the
development of such a flavor defect
 Phosphates
• Phosphates affect the absorption of calcium
and other elements
• The absorption of inorganic phosphorus
depends on the amount of Ca, Fe, Sr, and Al
present in the diet
• The danger in raising phosphorus levels is that
Ca may become unavailable
Use the Food Additives wisely based on the
scientific knowledge and reliable purposes