Food Additives

Antioxidants and Sweetners

 Food Additives
Food additives refer to any substances that are added to change food
in some way before it is consumed. Additives include preservatives
for extending shelf life, flavoring and coloring for improving taste
and appearance, and nutritional supplements such as vitamins and
minerals. The contaminants from manufacturing, storing and
packaging processes are also considered as indirect food additives.
⚫ Food stabilizers and emulsifiers such as lecithin, gelatins, corn
starch, waxes, gums, mono glyceride and propylene glycol
⚫ A number of different coloring agents such as annatto, cochineal,
and betanin
⚫ Anti-foaming agent for reducing the formation of foam in the
industrial process of liquids
⚫ Direct additives are added to a food for a specific
purpose and are identified on the ingredient label of
the food.
⚫ Indirect additives unintentionally become part of the
food in trace amount due to its handling, packaging,
transportation etc.
⚫ Excessive levels of an additive or inclusion of an
undeclared additive may be directly dangerous in
some instances.
 Migration of Packaging
⚫ Plastic consists of its polymer, plasticizers,
antistatic agents, stabilizers and antioxidants, etc.
⚫ Some components are more likely to migrate into
foods than others, esp. residual plastic monomers
and plasticizers.
⚫ The plastic monomers of most health concern are
vinyl chloride, and styrene.
 Types of Additives
⚫ Antioxidants
⚫ Sweeteners
⚫ Coloring Agents
⚫ Flavors
⚫ Flavor enhancers
⚫ Preservatives
⚫ Emulsifiers
⚫ Acids
⚫ Antimicrobial agents
Common food additives
⚫ Monosodium glutamate (MSG) for enhancing flavor
⚫ Artificial sweeteners such as aspartame, saccharine, and
sodium cyclamate
⚫ Preservatives in oily or fatty foods such as BHA, BHT, and
TBHQ
⚫ Preservatives in fruit juices such as benzoic acid, sodium
benzoate
⚫ Sulfites for stopping fermentation of beer, wine, and packaged
vegetables
⚫ Nitrates and nitrites in hot dogs and other meat products for
color retention
⚫ Antibiotics given to food producing animals
⚫ Food Colors natural and synthetic colors are used to adjust or
correct food discoloration or change during processing or
storage: Carotene, tartrazine, Riboflavin
Natural Food Additives
 Functions of Food additives
⚫ Prolong shelf life
⚫ Change/preserve color
⚫ Enhance flavor
⚫ Improve nutritional value
⚫ Compensate for vitamin and mineral deficiencies
⚫ Maintain freshness
⚫ Prevent spoilage
⚫ Facilitate food processing
Safety of Food additives
 Safety in Food additives
⚫ There are over 4000 food additives listed by the FDA used
every day and only 373 are considered GRAS (generally
recognized as safe)
⚫ The FDA banned the use of sulfites on raw fruits and
vegetables. Dangerous sulfites include sulfur dioxide,
potassium metabisulfite, sodium metabisulfite, potassium
bisulfite, sodium bisulfite and sodium sulfite.
Safety of food additives
⚫ Monosodium glutamate (MSG) which is added to food as
a flavor enhancer. Symptoms from it can include
headaches, nausea, rapid heartbeat, chest pains and
vomiting, as well as a tingling, numbness or burning
sensation along the neck, arms and face. Restaurants may
be using MSG without listing it–especially Asian
establishments.
⚫ Sodium benzoate is abundant in processed foods, from
fruit juices to pickles to hummus. Researchers believe it
may cause cell damage when combined with ascorbic acid
(vitamin c) because the pairing creates the chemical
benzene, a known carcinogen. Carcinogen means known
to cause cancer.
 Antioxidants
Antioxidants: antioxidant is any substance that, when present at
low concentrations compared with those of oxidizable substrate,
significantly delays or prevent oxidation of that substrate.

Today in terms of consumer point of view food quality is defined as

the over all acceptability which include better flavor, aroma and
appearance.

Many of the food ingredients contain unsaturated fatty acids which

are the main susceptible cause of increasing deterioration due to
oxidation. This can be delayed by adding additives in the form of
antioxidants.
 Background of antioxidants
Natural AO s
Synthetic AO s

Understanding importance
Prehistoric & Progress Changing consumer attitude of natural AO s
historic times

1920 – 1940 1950 – 1970 1970 – 1980 2014

Smoking meat, AO s as additives (gum guaiac, BHA, BHT, TBHQ, Spice antioxidants
fish & treating lecithin, tocopherols) PG, EDTA
food with spices

Natural treatment Natural additives Chemical compound Purified form of Natural AO s

 Ideal Antioxidants
No harmful physiological effects
Not contribute an objectionable flavor, odor, or color to the fat
Effective in low concentration
Fat-soluble
Carry-through effect No destruction during processing
Readily-available
Economical
Not absorbable by the body
 Characteristics of Antioxidants

The major antioxidants currently used in foods are

monohydroxy or polyhydroxy phenol compounds with
various ring substitutions. These compounds have low
activation energy to donate hydrogen. The resulting
antioxidant free radical does not initiate another free radical
due to the stabilization of delocalization of radical electron.

The resulting antioxidant free radical is not subject to rapid

oxidation due to its stability.

The antioxidant free radicals can also react with lipid

free radicals to form stable complex compounds
 Phenolic Antioxidants
⚫ They are used to protect fats against oxidation.
⚫ Butylated hydroxytoluene (BHT) and butylated
hydroxyanisole (BHA) are radical scavenger.
⚫ They interfere propagation step during lipid peroxidation.
⚫ These antioxidants can exhibit both antitumorigenic and
tumorigenic effects
⚫ BHA and BHT have low acute toxicity.
⚫ They are categorized as GRAS in FDA.
⚫ In 1980’s BHA was suspected to have carcinogenic
potential in animals and to be nongenotoxic should
have a threshold dose.
⚫ BHT metabolism is more complex and slower than
BHA. It is reported to have toxic effects on organ
systems.
⚫ However, BHA and BHT are still permitted to be used
in food 0.02% (200 ppm) of the fat oil content of
the food product or 50 ppm (combined BHA and BHT)
if they are used dry low-fat product.
 Antioxidants

OH
OH
C(CH3)3
(CH3)3C C(CH3)3

OCH3
CH3
Butylated Hydroxy Anisole Butylat Hydroxy
ed Toluene
 Antioxidan
OH
ts OH

OH OH C(CH3)3

COOC3H7 OH
PropGalla TBH
yl te Q

CHO OH OH CHO

OH OH
OH OH
CH3CH3
CH CH
CH3 CH3 CH3 CH3

Gossyp
ol
 Mechanism of Antioxidants
Hydrogen donation to free radicals by antioxidants.

Formation of a complex between the lipid radical and

the antioxidant radical (free radical acceptor).
Reaction of antioxidants with radicals

R∙ + AH RH + A∙

RO∙ + AH RO + A∙
H
RO ∙ + AH ROOH A∙
O +

R∙ + A∙ RA

RO∙ + A∙ ROA

RO ∙ + A∙ ROO
O A
Antioxidant +2 Oxidized
O Antioxidant
 Mechanism of Antioxidant

14 13 12 11 10 9
CH3 (CH2)3 CH2 CH CH CH2 CH CH CH2 R

Initiation Metal
Energy
-∙H Substrate
Reactive oxygen
effect
species
Lipoxygenase
13 12 11 10 9
CH3 (CH2) 4 CH CH CH CH CH CH2 R
∙
Ε0= 600mv Oxygen
+ O2 3
consumption,
K=109/se Conjugated diene
c
 13 12 11 10 9
CH3 (CH2)4 CH CH CH CH CH CH2 R

Propagation O
(K= 10o M-1sec-1)
O
∙
+ ∙ H from RH (triglyceride) .
0
R
Ε =1000m
v
(K= 107 M-1sec-1)
OH
C(CH3) O.
+∙Η 3
C(CH3)
3
from
OCH3
OCH3
Ε = 300-500mv
0
 13 12 11 10 9
CH3 (CH2)4 CH CH CH CH CH CH2 R
O
Peroxide O
value - ∙ OHMost reactive oxygen species
Transition Metal H
Ε0=2300 mv

13 12 11 10 9
CH3 (CH ) CH CH CH CH CH CH2 R
24
O
∙

Ε0=1600
Terminati mv
on CH3 (CH2) 4 CH Sensory evaluation
O Volatile compounds
CH3 (CH ) CH3
2 3
Antioxidant Safety

Food Additive Acts:

Total concentration of authorized antioxidants added

singly or in combination, must not exceed 200 parts pe
million by weight
on the basis of fat content of the food.
Application of Antioxidants to Foods

Direct addition of antioxidants to oil or melted fat.

Addition of antioxidants to the food after they are
diluted in oil.
Spraying antioxidant solution in oil on the food or
dipping food into antioxidant solution.
Natural vs Synthetic antioxidants
 Sources of Natural antioxidants

Source Bioactive constituents

Spices & Herbs Flavonoids, phenolic acids, coumarins
Teas Catechins and other condensed tannins
Fruits & Ascorbic acids, flavonoids, carotenoids,
vegetables hydroxylated carboxylic acids
Cereals & grains Flavonoids, phenolic acids, esters, lignans,
sterols
Oils & oilseeds Tocopherols, lignans, flavonoids, phenolic
acids, phospholipids
Legumes Isoflavonoids, phenolic acids
Proteins & protein Amino acids, peptides, carnosine, malliard
hydrolysates reaction products
Effect of antioxidant in edible oil

Pea nut oil

Time (Hr)
 Artificial and
Alternative Sweeteners
Molecular Basis of Sweetness

⚫ -OH groups
⚫ Acree and Shallenberger AH/B concept
 Acree and Shallenberger
⚫ (Shallenberger & Acree) published a paper entitled the
"Molecular Theory of Sweet Taste" in Nature [1969].
⚫ The model developed in that paper for sweetness was based
on a structure-activity relationship between the simplest
sweet tasting compounds and their structural features of the
stimulants and has become known as the AH-B theory.
⚫ The theory described with considerable success the structural
features necessary for sweetness, but it was not sufficient to
predict sweetness.
⚫ That is, not all compounds that satisfied the theory tasted
sweet nor was the theory able to predict potency level
especially for very high potency sweeteners.
⚫ However, all sweet compounds seemed to have an identifiable
AH-B feature.
Artificial and
Alternative Sweeteners
Artificial Sweeteners
⚫ Non-nutritive (no calories)
⚫ Cyclamate (banned in 1969)
⚫ Saccharin (Sweet ‘N Low, 300-fold)
⚫ Aspartame (warning label) = aspartic acid and
phenylalanine (180-fold)
⚫ Acesulfame-K (Sunette, 200-fold)
● Alitame (Aclame, 2,000-fold)
⚫ Sucralose (Splenda, 600-fold)
Sucralose
The perception of sweetness
is proposed to be due to a
chemical interaction that
takes place on the tongue…

Between a tastant molecule

and tongue receptor protein

THE AH/B THEORY OF SWEETNESS

A sweet tastant molecule (i.e. glucose) is called the AH+/B- “glycophore”.

It binds to the receptor B-/AH+ site through mechanisms that include
H-bonding.
AH+ /
B- γ
B
Glycophore

Hydrophobic interaction
AH

AH γ
B

Tongue receptor protein molecule

For sweetness to be perceived, a molecule needs to have certain requirements.

It must be soluble in the chemical environment of the receptor site on the
tongue. It must also have a certain molecular shape that will allow it to bond
to the receptor protein.

Lastly, the sugar must have the proper electronic distribution. This electronic
distribution is often referred to as the AH, B system. The present theory of
sweetness is AH-B-X (or gamma). There are three basic components
to a sweetener, and the three sites are often represented as a triangle.
 Identifying the AH+ and B-
regions of two sweet tastant
molecules: glucose and
saccharin.

Gamma (γ) sites are relatively hydrophobic functional groups

such as benzene rings, multiple CH2 groups, and CH3
 Sucralose
⚫ Splenda
⚫ 1998, approved for table-top sweetener and use in
various foods
⚫ Approved already in UK, Canada before US
⚫ Only one “made from sugar”
⚫ There was a law suit last year of this claim
⚫ Splenda lost….not a natural compound….a bit of a
deceptive marketing.
⚫ Clean, sweet taste and no undesirable off-flavor
Saccharin

⚫ Sweet’n Low, The 1st artificial sweetener

⚫ Accidentally found in 1879 by Remsen and Fahlberg
⚫ Saccharin use increased during wars due to sugar
rationing
⚫ By 1917, common table-top sweetener in America
⚫ Banned in 1977 due to safety issue
⚫ 1991, withdrew ban, but with warning label
⚫ 2000, removed warning label
⚫ Intensely sweet, but slight bitter aftertaste
Remsen-Fahlberg synthesis of saccharin
 Low Calories sweeteners
⚫ Low calorie sweeteners, such as saccharin,
aspartame, acesulfame.

Saccharin
⚫ It is 300 times sweeter than sugar.
⚫ It is not metabolized no calories.
⚫ It comes in the forms of pure saccharin,
ammonium saccharin, calcium saccharin, and
sodium saccharin.
⚫ Saccharin has low direct toxicity has a threshold.
⚫ It was allowed to be used in beverage additive at not
more than 12 mg/fluid ounce, not more than 30 mg
per serving as processed food additive.
⚫ ADI for saccharin is 2.5 mg/kg body weight.
⚫ But it has been implicated as a potential human
carcinogenic (since 1981), then it was de-listed as a
safe food additive.
⚫ In April 2000, saccharin was de-listed as a possible
human carcinogen due to the lack of data in humans
suggesting a carcinogenic hazard.
⚫ This decision caused a controversy. Another source
stated that saccharin correlated bladder cancer.
⚫ Saccharin-containing products are still required to
have warning statement on their labels.
Aspartame
⚫ Approved in 1981 as artificial sweetener.
⚫ It is 200 times sweeter than sugar and has the same
number of calories per teaspoonful.
⚫ Aspartame is a dipeptide consisting of L-aspartic acid
and the methyl ester of L-phenylalanine.
⚫ It can be hydrolyzed into aspartic acid, phenylalanine
and methanol during digestion.
⚫ Chronic methanol exposure can cause visual
impairment.
⚫ Phenylalanine can interfere with amino acid transport
and lead to nervous system disturbances only a
problem in people with the rare genetic disease
phenylketonuria (PKU) – unable to metabolize
phenylalanine properly.
⚫ When aspartame containing product are heated or stored
for a long period, aspartame can be decomposed into
diketopiperazine (DKP), a tumor agent.
⚫ ADI for DKP is 30 mg/kg bw.
⚫ ADI for aspartame is 50 mg/kg bw.
⚫ In ready to bake product aspartame is limited to 0.5% by
weight.
Aspartame
⚫ Nutrasweet, Equal
⚫ Discovered in 1965 by J. Schlatter
⚫ Composed of aspartic acid and phenylalanine
⚫ 4 kcal/g, but 200 times sweeter
⚫ Approved in 1981 for table-top sweetener and
powdered mixes
⚫ Safety debating
⚫ 1996, approved for use in all foods and beverage
⚫ Short shelf life, not stable at high temperature
 Acesulfame K
⚫ Sunette, Sweet One
⚫ Discovered in 1967 by Hoechst
⚫ 1992, approved for gum and dry foods
⚫ 1998, approved for liquid use
⚫ Blending with Aspartame due to synergistic effect
⚫ Stable at high temperature and long shelf life (3-4
years)
⚫ Bitter aftertaste
 Neotame
⚫ Brand new approved sweetener (Jan. 2000)
⚫ 7,000 ~ 13,000 times sweeter than sugar
⚫ Dipeptide methyl ester derivative; structurally
similar to Aspartame
⚫ Enhance sweetness and flavor
⚫ Baked goods, non-alcoholic beverages (including
soft drinks), chewing gum, confections and
frostings, frozen desserts, processed fruits and
fruit juices, toppings and syrups.
⚫ Safe for human consumption
Stevioside
⚫ A natural sweetener from Stevia rebuadiana plant.
⚫ It is 200-300 times sweeter than sugar and have no calories.
⚫ It was used as a common sweetener in Japan (herbal teas)
during 1980’s.
⚫ It was banned in 1991 because of the lack of formal toxicological
evaluation proving its safety.
⚫ It is not allowed in Canada and some EU.
⚫ Some current studies indicate that steviol, a metabolite of
stevioside may have toxic effect (EC).
⚫ Ironically, stevia is allowed as a nutritional supplement (FDA
Import Allert 45-06, 1996).
Licorice

Glycyrrhetic acid is an β amyrin derivative

- 50X sweeter than sucrose
- topical - anti - inflammatory property
increase foam in beer or root beer