FOOD

CHEMISTRY
PIGMENT
 Introduction
No matter how nutritious, flavorful, or well
textured a food, it is unlikely to be eaten unless
it has the right color.
Factors which influence the acceptability of
color in a certain food:

Culture

Geography

Sociology

No matter the biases or habits of a given area, certain

food groups are acceptable only if they fall within a
certain of color array
 Color acceptability  economic worth,
i.e. in many raw food materials

Color
 To denote the human eye’s perception of colored
materials,
 part of the electromagnetic spectrum visible to the
human eye and generally regarded as lying between 380
- 730 nm
i.e. red, blue, or green.
 Together with flavor and texture, color plays an
important role in food acceptability.
 Color is mainly a matter of transmission of light for clear
liquid foods, such as oils and beverages.
 Color may provide an indication of chemical changes in a

Pigment
food, such as browning and caramelization.
 Normal constituents of cells or tissues (which is
synthesized and accumulated in, or excreted from, living
cells) that impart color. It has other properties, i.e.
energy receptor, carriers of O2, protectants against
radiation

Colorant
 A general term referring to any chemical compound
(synthetically made) that impart (communicate)
color
i.e. dye & lake

Dye
 Colorants used in textile industry, has no place in food
usage.

Lake
 A food colorant is synthetically made, absorbed on the
surface of an inert carrier (i.e. alumina) and added to
processed foods
 referred to as certified colors

The colors of foods are the result of natural
pigments or of added colorants.

The natural pigments (non-certified colors) are a
group of substances present in animal and
vegetable products.

Four groups of natural pigments:
– tetrapyrrole compounds: chlorophylls, hemes, and
bilins
– isoprenoid derivatives: carotenoids
– benzopyran derivatives: anthocyanins and
flavonoids
– artefacts: melanoidins, caramels
 Non-Certified Colors (natural
colors)

Donot need certificate to sell or use.

Most are from nature (Natural Colors)

Members Include:
– Annatto extract
– Beet juice powder
– Canthaxanthin
– Caramel
 Non-Certified Colors (natural
colors)
– Beta-Apo-8’Carotenal
– Beta carotene
– Cochineal extract/carmine
– Grape color extract
– Grape skin extract
– Fruit Juice
 Non-Certified Colors (natural
colors)
– Vegetable juice
– Paprika oleoresin
– Riboflavin
– Titanium dioxide
– Turmeric
– Turmeric oleoresin
Artificial Color vs. Natural Color

Artificial Colors
Natural Colors
– Obtained by chemical – Obtained from nature
reactions – Processed by physical
means
– Relatively stable (in most
cases) – May be less stable than
synthetic ones
– Less costly to use
– May be more costly to use.
– Health concerns – No health concerns
 Allergens
– Benefits to health
 Cancer risks?
_ Consumer acceptability:
– Consumer acceptability: Good
Questionable
Pigments Indigenous to
Food
A. Chlorophylls
B. Myoglobin & Hemoglobin
C. Antocyanins
D. Carotenoids
E. Flavonoids
F. Proanthocyanidins
G. Tannins
H. Betalains
I. Quinones & Xanthones
J. Miscellaneous Natural Pigments
A. Chlorophylls
 Green pigments involved in the photosynthesis of higher plants,
incl. algae.

Location in plants
• In foods, concern focused on chlorophylls a & b  occur in
approximate ratio of 3 : 1
• In leaves, chlorophylls are located in plastid bodies, so called
chloroplasts (5-10 long µm; 1-2 thick µm)  within it are smaller
particles, called grana ( Ф 0.2-2 µm)  they are composed of
lamellae (Ф 0.01-0.02 µm)  chlorophylls molecule are surrounded
by lamellae.
 Physical Properties
• Chlorophyll a & pheophytin a  soluble in alcohol, ether, benzene
& acetone, slightly soluble in petroleum ether; insoluble in water.

• Chlorophyll b & pheophytin b  soluble in alcohol, ether, benzene

& acetone, almost insoluble in petroleum ether; insoluble in water.

Chemical properties
• In food processing, the most common alteration in green
chlorophylls  PHEOPHYTINIZATION; the replacement of the
central Mg by the hydrogen  form a dull olive-brown pheophytins.
- Mg ↓
Chlorophylls pheophytins
Effects in Food Handling, Processing & Storage
• Almost any types of food processing and/or storage  deterioration
of chlorophyll pigments.
• Dehydrated foods packed in clear containers  autooxidation  the
blanching degree before dehydration
• Lipoxygenases  produced free radicals  degraded the chlorophylls
• Fermentation of cucumber  produced pheophytins, chlorophyllides
& pheophorbides
• Heating of green veggies in acid condition  pheophytins production
Preservation of Green Color

The use of high quality materials  process as

quickly as possible  store the product at low
temperatures
B. Myoglobin & Hemoglobin
Myoglobin is a complex muscle proteins
Hemoglobin is the blood pigment
• Hb  contains 4 polypeptide chains & 4 heme groups, which
are planar collection of atoms with the iron atom at the center.
• Heme group function : to combine reversibly with a molecule
of O2  carried by the blood from the lungs to the tissues.
• Myoglobin  a quarter its size compared to Hb; consists of a
single polypeptide chain (±150 AA units) attached to a single Hb
group; it is contained within the cell tissues & it acts as a
temporary storehouse for the O2 brought by the Hb in blood.

Hb  considered the linking together of 4 myoglobins (the

discussion of these pigments can be limited to myoglobin)
Physical properties
• Myoglobin is part of sarcoplasmic proteins of
muscle; soluble in water & dilute salt solution.

Chemical Properties
• Oxygenation reaction
Myoglobin + molecular O2  oxymyoglobin (O2Mb) forms bright red
pigment
• Oxidation reaction
Myoglobin oxidation  metmyoglobin (MMb) forms brown color

• Ferrous covalent complexes of myoglobin (purple) with :

- Molecular O2  oxymyoglobin
- Nitric oxide  nitrosomyoglobin
- Carbonmonoxide  carboxymyoglobin
Effect of Handling, Processing & Storage
• Cured Meat Pigment

In commercial practice, sodium nitrite (NaNO2) is the source of nitrous acid:

NaNO2 (salt cure) in water  Na+ + NO2 - (nitrite ion)  HNO2 (in the
curing brine)

Or using combustion gas (NO2) to smoke or gas-oven fresh meat:

2 NO2 (gas cure) + H2O (in meat) ---> HNO2 (nitrous acid) +
HNO3 (nitric acid)

Meat Curing:
HNO2 + Mb (myoglobin in meat)  NOMb (pink cured meat pigment)
The formation of cured meat pigments viewed as 2 processes:
(1) Biochemical reaction, which reduce nitrite  nitric oxide; iron in
heme  the ferrous state

(2) Thermal denaturation of globin  heating at 66 C or higher & may

involve the coprecipitation of the heme pigment with other protein
in meat
• Packaging
Because meat pigment easily reacts with oxygen to
produce either an acceptable oxygenated products
or unacceptable oxidized products

• Carbon monoxide (CO) flushing

It was done before sealing of fresh beef  very effective for
preserving & stabilizing color for 15 days

Certain metallic ions (esp. Cu)  extremely active in promoting

autooxidation of O2Mb to MMb, while Fe, Zn, Al are less active
C. Anthocyanins
 A group of reddish water-soluble pigments in plants which exist
in the cell sap/juice, i.e. flowers, fruits, vegetables,
• An anthocyanin pigment is composed of an aglycone (an
anthocyanidin) esterified to 1 or more sugars. Only 5 type of sugars
found in it, which are, in order of relative abundance : glucose,
rhamnose, galactose, xylose, arabinose

• Anthocyanins may also be “acylated” which adds a third component

to the molecule, i.e. p-coumaric, ferulic, caffeic, malonic, vanillic, or
acetic acids may be esterified to the sugar molecule.

Fig. Anthocyanin aglicone

Stability in Food
• Anthocyanins show a marked change in color with changed in pH
 the higher the pH  the faster the rate of destruction

Chemical Reactions
• The addition of sulfite, sulfite oxide  rapid bleaching of the
anthocyanins  yellowish colors.
i.e. in the making of jams, preserves such as dried fruits &
vegetables

• The reaction with ascorbic acid  the degradation of both

compounds  the intermediate, peroxide produces by ascorbic acid
degradation
i.e. Cranberry juice cocktail stored at room temperature:
0 days – 9 mg/100 g anthocyanins & 18 mg/100 g ascorbic acid
6 months – ascorbic acid degradation & 80% degradation of anthocyanin
D. Carotenoids
 A group of mainly lipid soluble compounds responsible of the
yellow & red colors of plants & animal products.
• Most of produced carotenoids in nature is in form of fucoxanthin in
various algae, in green leaves : lutein, violaxanthin, neoxanthin; β-
carotene; lycopene in tomatoes; capxanthin in red peppers

LUTEIN
kiwi, egg yolk, corn, zucchini, red grapes, pumpkin

Good for
• Carotenoids include a class of HC, called carotenes, and their
oxygenated derivatives, called xanthophylls.
• They consist of 8 isoprenoids units joined in such a manner that the
arrangement of isoprenoid units is reversed in the center of the
molecule.

• Forms of carotenoids :
(1) free state in plant tissues (crystals or amorphous solids
(2) solution in lipid media, i.e. capxanthin- lauric acid ester
in paprika
Fig. Red pigment of astaxanthin Fig. Mud crab Fig. Lobster

• The association of carotenoids with proteins stabilised the pigment

& also change the color, i.e. red carotenoid astaxanthin when
complexed with protein  blue colorant in lobster shells; ovoverdin,
the green pigment in lobster eggs; carotenoid-protein complexes
found in fruits, vegetables.

• Carotenoids may occur in combination with reducing sugars via a

glycosidic bond, i.e. CROCIN - containing 2 molecules of the sugar
gentiobiose united with crocetin, found as the main pigment in
SAFFRON
Chemical Reactions

Provitamin A
• Beta carotene is precursor of vitamin A, which yields 2 molecules
of vitamin A by cleavage at the center of the molecule.
• Alpha carotene is precursor of one molecule of vitamin A; which
is half identical to beta carotene.

Oxidation reaction
• Stability of carotenoids depend on whether the pigment is in vivo
or in vitro in environmental condition, i.e. lycopene in tomatoes is
quite stable, but the extracted purified pigment is unstable.
• Enzyme degraded carotenoids rapidly, i.e. lypoxygenase.
• In processed food  heat, light, presence of pro- and antioxidant
influence carotenoids degradation.
Non-certified Colors
(Natural Colors)

Food processing applications

 Annato

Annatto extract.
– Extracted from annatto seeds, Bixa orellna L.,
a tropical bush.
 Annatto

– Two forms commercially available:

 Bixin.
 Annatto

Bixin
– Color in final foods: orange.
– Solubility: oil soluble.
– Stability:
 Light stability: Fair.
 Heat Stability: good under 130 oC.
– Application: fatty or oily foods, including
snack, cake & other bakery products, butter,
popcorn oil.

Norbixin
 Solubility
 water soluble in neutral or alkaline solution
 Precipitates in acidic solutions (pH<5).
 Stability
 Light stability: fair
 Heat Stability: good under 130 oC
 Acid stability: poor
 Application: cheese, bakery, snacks, confectionery,
etc.
 Annatto

Acid-stable annatto emulsion for beverages

 Beet Juice Concentrate
– Obtained from red
Solubility: water
beet roots soluble
 Beet Juice Concentrate
– Stability:
 Light: good
 Heat: Poor. Will not survive during heat processing
in most cases
 pH: almost no effect
 Beet Juice Concentrate

– Applications:
 Ice Cream
 Ice bar
 Hard candy
 Dry Beverage mixes (in powder form)
 Noodle/pasta
 Beta carotene/natural mixed
carotenes

Syntheticor extracted from natural source,
plants or algae
Beta carotene/natural mixed
carotenes
– Solubility – Stability:
 Oil soluble  Heat stability: Good
 Our Solution: Made  Light stability: Poor
water-dispersible.
 Beta carotene/natural mixed
carotenes
Stabilization.
Left: ACRC,
Right: A
competitor’s product.
Both were exposed
to sunlight for 5 days

Photo 1.Stability comparison. Both were boiled, hot filled and exposed to outdoor direct sunlight for 5 days. PH 2.3
Left : ACRC natural carotenes.
Right: Control (a competitor’s sample)
 Caramel

Source:
– Reaction products of carbohydrates during heating
– Usually ammonium and sulfate are added
 Negatively charged
 Positively charged

Stability
– Light: very stable
– Heat: very stable
– Acid: use acid stable type

Application:
– Beverages
– Bakery
– Confectionery
– Snacks, etc
 Cochineal Extract

Source
– Extracted from cochineal (dactylopius
coccus costa)
 Cochineal Extract

Stability
Acid stable cochineal
extract:
– Light: excellent
– Can be boiled in 10%
– Heat: excellent citric acid or even 0.01N
– pH: poor HCl for at least 3 hrs.
 Orange in acidic pH – Dose not precipitate in
 Purple in neutral pH acidic beverage 
 Blue in alkaline pH precipate cause
discoloration.
 Cochineal Extract

Left: Control (An acid proof cochineal extract from a competitor) in 0.3% citric acid solution.
The original red color faded away after exposure.
Center: ACRC 1162-ralb in 1.0% citric acid solution. The original red color did not fade.
Right: ACRC 1162-ralb in 0.01N HCL. The original red color did not fade.
 Carmine

Source:
– Aluminum/calcium lake
of carminic acid, the
coloring component in
cochineal extract
– In powder form,
insoluble in water,
Carmine is not acid stable:
soluble in alkaline – Discoloration
water. – Preciptitation

Application: pasta, surimi,
bakery-pie fillings,
seafood, bakery, pudding
 Grape Color Extract

Sources:
Stability:
– Extract of precipitated – Light: good
lees of Concord grape
 Heat: fair
juice during storage
 pH: poor

Solubility:
– Acidic: red to
– Water purple
– Neutral: purple
– Alkaline: blue
 Grape Color Extract

Applications:
– Non-beverage foods
 Pie filling
 Fruit preparation
 others
Grape Skin Extract (Enochianina)

Source
Stability:
– Extract of deseeded – Light: good
marc, remaining after  Heat: fair
grapes have been  pH: poor
pressed for juice or – Acidic: red to
wine. purple
– Neutral: purple

Solubility: – Alkaline: blue
– water
Application:
– Beverages (alcoholic,
carbonated)
 Fruit juice

Source:
Solubility: water

– Mature, edible fruits
Stability:
 Elderberry – Light: good
 Black currant
– Heat: fair
 Blackberry
– pH: color changes heavily
 Others
as pH changes

Coloring agent:  Acidic: red
anthocyanins  Neutral: purple

Applications:  Alkaline: Blue
– Beverages - the lower pH the darker
– Tomato paste the color
– Fruit preparation - Ascorbic acid accelerates
anthocyanin degradation.
 Vegetable Juice

Source:
– Fresh or dehydrated vegetables
 Red cabbage
 Red radish
 Black carrot
 Purple yam
 Vegetable juice

Coloring components
Stability:
– Anthocyanins – Light: good

Solubility: water – Heat: fair
– pH: color changes
heavily as pH changes
(the lower the pH is,
the more condense the
color is)
 Acidic: red
 Neutral: purple
 Alkaline: Blue
 Cabbage Color

One of the most stable anthocyanin

colors

Purplish red in acidic solution

Low odor version available

Both liquid and powder forms
available
 Cabbage Color

Wide applications
– Beverage
– Tomato paste
– Pizza topping
– Fruit preparations
– Snack foods
– Dairy
– Confectionery
 Red Radish Color

One of the most stable anthocyanin colors

red in acidic solution

Low odor version available

Both liquid and powder forms
available
 Red Radish Color

Keeps red at higher
Wide applications

pH up to 6 – Beverage
– Tomato paste
– Pizza topping
– Fruit preparations
– Snack foods
– Dairy
– Confectionery

0038-ralb in a model rice beverage, pH 6.0

 Paprika Oleoresin

Source:
Solubility:
– Extracted from red – Oil soluble
pepper

–ACRC made it
water dispersible
 Paprika Oleoresin

Stability
Applications:
– Light: Fair. – Seasoning
– Heat: good – Snack
– Salad dressing
– Popcorn
– Beverage
– Confectionery
– Others
 Turmeric Oleoresin (Curcumin)

Source:
Coloring component:

– Extracted from – Curcumin and
curcuma longa L., a curcuminoids
member of ginger
Solubility
family.
– Fat and alcohol soluble
– Cold water insoluble
– Commercially dissolve
curcumin in
polysorbate-80 or –60
to make it water
dispersible
 Turmeric Oleoresin (Curcumin)

Stability:
Color hue: Bright

– Heat: good yellow in acidic
– Light: poor solution
– pH: color hue change
with pH
 Greenish in acidic pH
 Orange yellow in
neutral pH
 More stable in acidic pH
than in neutral or
alkaline pH
 Turmeric Oleoresin (Curcumin)

Applications: – Snack
– Pickle – Pudding
– Bakery – Gelatin
– Confectionery – Gummy bear
– Others – Yogurt
– Popcorn
– Finger foods
 Lutein

A member of
Reasons to use lutein
carotenoids – Extended studies have

Solubility: proved the
importance of lutein to
– Oil soluble
eye health
– We made it
– Antioxidant--a free
water-dispersible radical scavenger
Lutein

Applications
– As a nutritional
supplement
can be added to all
foods
(plain in taste and
flavor)
– As a natural colorant:
can be added to all
food
(a bright yellow color in
water solution)
 Lycopene

Sources:
– Synthetic
– Extracted from nature,
plants or
microorganisms

A member of
carotenoids
 Lycopene

Solubility

Oil soluble by nature

ACRC has made
stabilized and water-
dispersible
lycopene — for
beverage and other
food applications
 Lycopene

Properties
Applications
– Benefit to prevent – As a nutritional
prostate cancer supplement,
– An antioxidant—free It can fortify every
radical scavenger food.
– Beautiful orange color – As a natural colorant,
in beverage it can color every food