TANNINS & LIPIDS

TANNINS Witch Hazel (Hamamelis virginiana)

Tannins are phenolic plant secondary

compounds and are widely distributed through
the plant kingdom, especially legumes and
browse which affect animal performance in
many countries. Non-Crystallizable
Hamamelis Water
hydrocolloid mixture of polyphenols
● Distilled Witch Hazel Extract
● Distillation of recently cut and partially
Two Types of Tannins
dried dormand twigs of Hamamelis
● HYDROLYZABLE tannins
● Hydroalcoholic solution containing
● NON- HYDROLYZABLE tannins
volatile oil
Uses: Astringent in hemorrhoidal products
Astringent in insect bites,and sting
preparation
Astringent in teething preparations

Tannins Properties:
● Forms colloidal solution in water 1. NUTGALL
● Acid reaction ● Hardened excrescence from the young
● Puckering Taste twigs of Quercus infectoria when a
● Precipitated by copper. lead, tin, Hymenopterous insect (Cynips tinctoria)
dichromate bores holes to deposit its ova
● Precipitates gelatin
● Precipitates alkaloid to form insoluble
tannates
Tannins uses:
● Astringent
● Carcinogenic Potential
2. TANNIC ACID
● Converts añimal hide to leather
● Gallotannic acid, Tannin
● Nutgall is the most important source,
Tannins
also gallic and ellagic acid
1. HAMAMELIS LEAF
● Solvent extraction of powdered galls-
AKA: Witch Hazel (Hamamelis virginiana)
aqueous: gallotannin, ethereal: free
Constituents : Hammamelitannin
gallic acid
(derived form: gallic acid)
● Component of Universal Antidote
Use: Astringent and hemostatic
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UNIVERSAL ANTIDOTE
● Activated charcoal (8 grams) (2 parts)
- to absorb poison
● Tannic Acid (4 grams) (1part)
- To convert Poison
● Magnesium Oxide (4 grams) (1 part)
- To act as a catalyst.
DISSOLVE THE ABOVE COMBINATION IN 1
GLASS OF WATER AND ADMINISTER.
TANNIC ACID Uses:
● As astringent, treatment of burns,
topical application for bed sores, minor
ulcerations, for alkaloidal poisoning
● Also used in tanning and dyeing
industries
● Manufacture of inks
3. JAPANESE and CHINESE GALLS
● Formed on Rhus chinensis by stings of a
plant lice (Aphis)
Uses: manufacturing of gallic acid
(aka: 3,4.5-trihydroxybenzoic acid)
● Prepared from tannic acid by hydrolysis
● Bismuth subgallate: used to help control
odors
- deodorizer for flatulence
- antacid
Other source : Guava, Duhat, Kamachile
(barks & roots)
LIPIDS
LIPIDS - esters of long chain fatty acids and
alcohol
FORMS
● Fixed oils- unsaturated esters of fatty
acid + glycerol
● Fats - saturated esters of fatty acid +
glycerol
● Waxes esters of HMW alcohols + fatty
acids
● Prostaglandins - lipid alcohol
Classification of lipids
Lipids
● Lipids (fixed oils, fats, and waxes) are
esters of long-chain fatty acids and
alcohols, or of closely related
derivatives.
● The chief difference between these
substances is the type of alcohol:
1. In fixed oils and fats, the alcohol is
glycerol,combined with the fatty acids.
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2. In waxes, the alcohol has a higher
molecular weight, e.g., cetyl alcohol
(CH,(CH,)gOH).
FIXED OILS
Fixed oils - are unsaturated esters of fatty
acid with glycerol.
Figure 1. Structure of Glycerol
Fixed oils and fats
● Fats and oils are made from two kinds of
molecules:
● glycerol (a type of alcohol with a
hydroxyl group on each of its three
carbons) and three fatty acids joined by
dehydration synthesis. Since there are
three fatty acids attached, they are
known as triglycerides.
Where R, R', and R° are long alkyl chains; the
three fatty acids RCOOH, R'COOII and R"COOH
can be all different, all the same, or only two
the same
Structure Fats and Fixed Oil
Structure: glycerol (3C alcohol) + fatty acid
fatty acid = long HC "tail" with COOH
group at "head"
CHEMISTRY OF FIXED OILS:
-Fixed oils are esters of fatty acid with glycerol.
- These May be: Monoglycerides
Diglycerides
Triglycerides
Triacylglycerol
● 3 fatty acids linked to glycerol
● ester linkage = between OH & COOH
(b) Fat molecule (triacylglycerol)
● The "tall" of a fatty acid is a long
hydrocarbon chain, making it
hydrophobic
● The "head" of the molecule is a carboxyl
group which is hydrophilic
● Fatty acids are the main component of
soap, where their tails are soluble in oily
dirt and their heads are soluble in water
to emulsify and wash away the oily dirt.
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● However, when the head end is attached IODINE VALUE

to glycerol to form a fat, that whole
molecule is hydrophobic.
PROPERTIES OF FIXED OILS
● Non-irritant
● Odorless
● Tasteless
● Non-volatile
● Insoluble in water and soluble in organic
solvents
● Produce greasy mark on paper
● Upon heating strongly, undergo
decomposition
● Upon hydrolysis, yield glycerol and fatty
acid
CLASSIFICATION OF FIXED OILS:
- On the basis of their ability to absorb
oxygen from air:
1. Drying oil - When exposed to air,
undergo oxidation and form, tough and
hard film. These are usually used in
paints and varnishes.
2. Non-drying oil - These oils neither
undergomoxidation nor form tough and
hard film.
3. Semi-drying oil- When exposed to air,
undergo a little bit of oxidation and
form a tough and thin film.
Aka lodine Number, in analytical
chemistry, measure of the degree of
unsaturation of an oil, fat, or wax.
The amount of iodine, in grams, is taken
up by 100 grams of the oil, fat, or wax.
Saturated oils, fats, and waxes take up
no iodine; therefore their iodine value is zero;
but unsaturated oils, fats, and waxes take up
iodine. (Unsaturated compounds contain
molecules with double or triple bonds, which
are very reactive toward iodine.)
The more iodine is attached, the higher
is the iodine value, and the more reactive, less
stable,softer, and more susceptible to oxidation
and rancidification is the oil, fat, or wax.
In performing the test, a known excess
of iodine, usually in the form of iodine
monochloride, is allowed to react with a known
weight of the oil, fat, or wax, and then the
amount of iodine remaining unreacted is
determined by titration.
METHODS OF OBTAINING FIXED OILS
- Fixed oils and fats of vegetable origin
are obtained by:
1. Extraction by expression
- Fixed oil is obtained by expression in
hydraulic presses. If the expression is carried
out in the cold, the oil is known as a "virgin oil"
or a "cold-pressed oil." In contrast, if the
expression is carried out in heat, the oif is
known as a "hot-pressed oil."

Types of Fixed Oils based on lodine Value

Type I.V. Example

Non-drying < 100 Olive, Almond

Semi-drying 100-120 Cottonseed, Sesame

Drying >120 Cod Liver Oil, Linseed

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2. Extraction by solvents COLLECTION OF COTTONSEED OIL:

- Sometimes organic solvents are used for the
extraction of oils.

Cottonseed Oil Plant, Cottonseed Oil

Production Line, Cottonseed Oil Equipment

Animal fats are separated from other tissues by

rendering with steam, with or without
pressure. The heat melts the fat, which rises to
the top and may be separated by decantation Constituents of Cottonseed oil:
Glycerides of: Linoleic acid
USES OF FIXED OILS AND FATS: Oleic acid
1. Soap manufacturing, Palmitic acid
2. Suppositores, tablet coating Stearic acid
3. Dietary supplements Arachidic acid
4. Emulsifying agents Myristic acid
5. Manufacture of paints, varnishes and Uses of Cottonseed oil:
lubricants ● Food Emollient Vehicle for injections
6. Therapeutic uses (castor oil). ● Preparation of hydrogenated vegetable
oils
1. COTTONSEED OIL ● Soap manufacture
Botanical origin: Gossypium herbaceum
Family: Malvaceae Toxicity of Cottonseed oil:
Part used: Seeds - Occur due to intravenous administration of
cottonseed oil emulsion.
Acute toxicity includes following symptoms:
-Fever - Headache
- Pain in back or chest - Tachycardia
- Nausea - Dizziness
- Vomiting
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Chronic toxicity includes following symptoms; Toxicity of Castor Oil:

- GIT bleeding ● Excessive oral administration in larger
- Mild anaemia doses results in toxicity.
- Defects in blood clotting Symptoms include: - Nausea
Treatment of toxicity: - Colic
- IV hydrocortisone sodium succinate 50g - Vomiting
- Promethazine 50mg - severe purgation
- Heparin (to aid clearance of fat from - Electrolyte imbalance
circulation)
3. LINSEED OIL
2. CASTOR OIL ➢ Also known as flaxseed oil or flax oll, is a
CN: Tangan-tangan colorless to yellowish oil obtained from
SN: Ricinus communis the dried, ripened seeds of the flax plant
Family:　 Euphorbeaceae (Linum usitatissimum).
Part used: seeds Botanical origin: Linum usitatissimum
Family: Linaceae
Constituents: Triricinolein → Ricinoleic Acid Part used: Seeds
(F.A.); Ricin - toxic
Undecylenic Acid - product of pyrolysis Linum usitatissimum Linseed/Flaxseed Oil
of castor oil (antifungal)
Ricinus communis

Collection of Castor Oil:

Constituents of Linseed Oil

Glycerides of: Isolinoleic acid
Linoleic acid
Chemical Constituents of Castor Oil: Stearic acid
Glycerides of: Ricinoleic acid Myristic acid
Ricinoleic acid Palmitic acid
Oleic acid Uses of Linseed oil:
Linoleic acid ● In veterinary medicine as Purgative
Stearic acid
Uses of Castor Oil: 4. OLIVE OIL
- Purgative CN: Sweet oil, Oil of Europe
- Emollient SN: Olea europaea
- Emollient Preparation of zinc and castor oil Family: Oleaceae
- Preparation of zinc and castor oil ointment Part used: Ripe fruit
- Sterilized castor oil as soothing agent in eye
- Oily vehicle for eye drops

Forms:
Virgin-10w temp is used (cold press
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Tournant - fallen or decomposing fruit 6. CORN OIL

Technical - boiling water Botanical origin: Zea mays
Sulfur - carbon disulfide for extraction Family: Gramineae
Part used: Embryo
Adulterant:
Tea tree oil/ Camelia oil (Camellia sinensis) Constituents of Corn Oil:
Glycerides of: Oleic acid
Constituents of Olive Oil: Linoleic acid
Glycerides of: Oleic acid Stearic acid
Linoleic acid Arachidic acid
Stearic acid Palmitic acid
Arachidic acid Myristic acid
Palmitic acid Lignoceric acid
Uses: Laxative Uses:
Nutrient ● Vehicles in pharmaceutical and
Emollient cosmetic preparation
Demulcent ● Solvent for injections
● Nutrient
5. PEANUT OIL
● akar Arachis Oil 7. SWEET ALMOND OIL
● non-containing oil Botanical origin: Prunus amygdalus
(contains more saturated FA) Family: Rosaceae
Botanical origin: Arachis hypogaea Part used: Seeds
Family: Leguminosae Almond (Prunus dulcis/Prunus amygdalus
Part used: Seeds

Constituents of Almond Oil:

Constituents of Peanut Oil:
Glycerides of: Oleic acid
Glycerides of: Oleic acid
Linoleic acid
Linoleic acid
Palmitic acid
Stearic acid
Myristic acid
Arachidic acid
Uses: Nutrient
Palmitic acid
Demulcent
Behenic acid
Emollient
Lignoceric acid
Preparation of cold creams, hair lotions
Uses:
and toilet articles
● Vehicles in emulsions, liniments,
plasters, soap
● Ink manufacture
● Preparation of hydrogenated vegetable
oil
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8. SESAME OIL 11. SUNFLOWER OIL

Botanical origin: Sesamum indicum Botanical origin: Helianthus annuus
CN: Teel or Benne Oil Family: Compositae
Family: Pedaliacea Part used: Seeds

Part used: Seeds

Constituents: Sesamol
12. Mustard Oil
Botanical origin: Brassica juncea
Family: Cruciferae
Part used: Seeds

9. COCONUT OIL
Botanical origin: Cocos nucifera
Family: Palmae
Part used: Dried solid part of endosperm
OFFICIAL OILS
Constituents of Coconut Oil: 1. Corn - mais (Zea mays); Fam. Fabaceae
Glycerides of: Lauric acid 2. Cottonseed - Gossypium hirsutum;
Myristic acid Fam: (Malvaceae)
Capric acid ● Gossypol - male contraceptive/
Caprylied acid destroys semeniferous ducts
Caproic acid 3. Peanut - Arachis hypogaea (Arachis Oil)
Oleic acid ● non-containing oil (contains more
Palmitic acid saturated FA)
Stearic acid 4. Sesame Oil
Uses: Nutrient
Confectionaries OTHER SOURCES OF FIXED OIL
Cosmetics ● Persic Oil (Apricot)
Ointment base ● Ethiodized Oil Injection - product of
poppy seed (Papaver somniferum) oil (I2
10. SAFFLOWER OIL addition)
Botanical origin: Carthamus tinctorius ○ radiopaque material
Family: Compositae ● Theobroma Oil - Food of the gods
Part used: Seeds ○ SN: Theobroma cacao
○ Suppository Base
■ a - melts at RT
■ B- melts at temp lower
than body temp (solid at
RT)
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FATS
● generally solid at room temperature
Fats and fatty acids
The terms saturated, unsaturated
(mono-unsaturated, and poly-unsaturated)
refer to the number of hydrogens attached to
the hydrocarbon tails of the fatty acids as
compared to the number of double bonds
between carbon atoms in the tail
1) Saturated fats
➢ Fats, which are mostly from animal
sources, have all single bonds between
the carbons in their fatty acid tails
➢ All the fatty acids in these triglycerides
contain the maximum possible amount
of hydrogens, these would be called
saturated fats.
➢ The hydrocarbon chains in these fatty
acids are, thus, fairly straight and can
pack closely together, making these fats
solid at room temperature.
➢ solid at room temp. contributes to
cardiovascular disease (atherosclerosis)
= plaque deposit
2) Unsaturated fats
➢ Oils, mostly from plant sources, have
some double bonds between some of
the carbons in the hydrocarbon tail,
causing bends or "kinks" in the shape of
the molecules.
➢ Because some of the carbons share
double bonds, they're not bonded to as
many hydrogens as they could if they
weren't double bonded to each other.
Therefore these oils are called
unsaturated fats.
➢ Because of the kinks in the hydrocarbon
tails, unsaturated fats (or oils) can't pack
as closely together, making them liquid
at room temperature.
➢ In unsaturated fatty acids, there are two
ways the pieces of the hydrocarbon tail
can be arranged around a C=C double
bond (cis and trans).
➢ In cis bonds, the two pieces of the
carbon chain on either side of the
double bond are either both "up" or both
"down," such that both are on the same
side of the molecule.
➢ In trans bonds, the two pieces of the
molecules are on opposite sides of the
double bond, that is, "up and one "down"
across from each other.
➢ Naturally-occurring unsaturated
vegetable oils have almost all cis bonds,
but using oil for frying causes some of
the cis bonds to convert to trans bonds
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What is the difference between cis and trans FATS VS FIXED OILS
fats?(VIDEO)
Fats Fixed oils

Solid at room temp Liquid at room temp

Contain saturated Contain unsaturated

Important about Fats
glycerides e.g. glycerides e.g.
● If oil is used only once like when you fry
glyceryl stearate glyceryl oleate
an egg, only a few of the bonds do this
so it's not too bad. However, if oil is
WAXES
constantly reused, like in fast food
● esters of long chain fatty acids and
French fry machines, more and more of
HMW alcohols
the cis bonds are changed to trans until
● Like fats, waxes are esters of fatty acids.
significant numbers of fatty acids with
● The alcohol, however, is not glycerol but
trans bonds build up. The reason for this
usually a long-chain, high molecular
concern is that fatty acids with trans
weight alcohol.
bonds are carcinogenic, or
● In plants, waxes are generally found
cancer-causing.
covering the external parts, like the
● Although most vegetable oils are liquid
epidermis of leaves and fruits, where
at ordinary temperatures and most
their main function is to prevent the
animal fats are solid, there are notable
loss of water. (Cuticle)
exceptions, such as cocoa butter, which
● Wax is also produced by insects, e.g. the
is a solid vegetable oil, and cod liver oil,
honeycombs of bees and wasps.
which is a liquid animal fat.
● Jojoba wax ,Carnauba wax, Beeswax
● Trans-fatty acids are found in fried
● Wax is used in pharmacies to make soft
foods, commercial baked goods,
ointments harder and to prepare lip
processed foods and margarine
salves.

1. LANOLIN
● obtained from sheep's wool (Ovis aries)
● Lanolin (Hydrous Wool Fat) -
20-25% moisture
● Anhydrous Lanolin (Wool Fat) -
0.25%　moisture - penetrates faster

2. HYDROGENATED VEGETABLE OIL

● solid
● oil that is solidified, deodorized　and
decolorized

3. COD LIVER OIL

● fat that is liquid at room　temperature
Source: Atlantic cod (Gadus morhua)
● Na marrhuate (FA)
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Difference between Waxes and fixed oils and fats
● Wax has a melting point above
approximately 45 °C (which
differentiates waxes from fats and oils).
● Fats and oils may be saponified by
means of either aqueous or alcoholic
alkali but waxes are only saponified by
alcoholic alkali. (this fact is used for the
detection of fats when added as
adulterants to waxes).
PLANT SOURCES
1. CARNAUBA WAX
● also called Brazil wax or ceara wax, a
vegetable wax obtained from the fronds
of the carnauba tree (Copernicia
cerifera) of Brazil.
● Valued among the natural waxes for its
hardness and high melting temperature,
carnauba wax is employed as a
food-grade polish and as a hardening or
gelling agent in a number of products.
Carnauba wax
Carnauba Palm (Copernicia prunifera or
Copernicia cerifera)
2. JOJOBA OIL - Liquid plant wax
SN: extracted from the seeds of the
jojoba plant (Simmondsia chinensis)
● solidified form resembles spermaceti
ANIMAL SOURCES
1. SPERMACETI WAX
● from sperm whale
(Physeter macrocephalus)
● Ambergris (whale ambergris or grey
amber) - crude material; was a fixative
that prevented fragrance from
evaporating.
● Synthetic wax substance :
Cetyl ester wax
SPERMACETI WAXES
DID YOU KNOW?
The name of the SPERM WHALE comes
from the word spermaceti (“sperma” means
sperm/semen; “cet” means whale, in Latin).
Spermaceti is a semi-liquid waxy substance
that is present largely within the head cavity of
the animal (in its spermaceti organ and junk).
The name was given due to its close
resemblance to semen but in fact, spermaceti is
NOT the semen of the whale, rather, it assists
in the animal's buoyancy control and
echolocation. Spermaceti oil was highly
demanded back in the 19th and 20th centuries
for making candles, lamp oil and lubricant.
Spermaceti, a wax liquid at body
temperature, obtained from the head of a
sperm whale or bottlenose whale. Spermaceti
was used chiefly in ointments, cosmetic
creams, fine wax candles, pomades, and textile
finishing; later it was used for industrial
lubricants. The substance was named in the
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mistaken belief that it was the coagulated
semen of the whale.
The fluid contained in the spermaceti
organ of the whale's head was removed to
obtain crude sperm oil. The spermaceti was
separated from the oil by chilling in a process
whalers called wintering; it congealed as a
white crystalline, waxy solid.
Chemically, pure spermaceti consists
principally of CETYL PALMITATE and other
esters of fatty acids with fatty alcohols and
melts at about 44°C (111° F).
2. BEES WAX
● from the honeycomb of the honey bee
(Apis mellifera)
2 forms: White beeswax (decolorized)
Yellow beeswax
USP OFFICIAL TESTS FOR EIXED OIL
1. Acid Value
2. Ester Value
3. Saponification Value
4. lodine Value
1. Acid Value
● the number of mg of KOH required to
completely neutralize free fatty acids
present in 1 gram of fat or oil.
● It is a relative measure of rancidity as
free fatty acids are normally formed
during decomposition of oil glycerides.
● The value is also expressed as percent of
free fatty acids calculated as oleic acid.
Significance:
1. Oils decompose on long standing due to
bacterial/fungal contamination or
chemical decomposition.
● Acid number is higher for oils stored for
longer duration (manufacturing
/packing date important)
2. Acid Number : Refined oils should be
free from any free fatty acids & have
negligible acid number (AN - nil )
Principle:
● The acid value is determined by directly
titrating the oil/fat in an alcoholic
medium against standard KOH/NaOH
solution.
Rancidity:
● fat/oil undergoes oxidation →
producing undesired/dangerous
metabolites-imparting unpleasant odor
to stored fat/oils. Certain factors
aggravate oxidation of fat /oils.
● condition reached in certain food as the
lipid material (fat) undergoes oxidation
reactions producing aldehydes, hydroxyl
acids, keto acids, and other compounds
which are responsible for the odor and
off-flavour producing stale food.
Factors causing rancidity
Light Water
Oxygen Molds
Trace elements Bacteria
Salt
Determination of Acid number:
using titration of a stored oil with alkali
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Neutralization point for detection of Acid No. 4. lODINE VALUE

Neutralization Point
● determines Acidity or Alkalinity of oil.
● Acidity/Acid value/Acid number is mgs
of KOH réquired to neutralize acid in
1gm of oil.
● Alkalinity/Base value/Base number is
mgs of acid required to neutralize all
bases in 1 gm oil.
● As the Neutralization Point of oil
increases, the age of oil decreases.
● lodine number is defined as the grams
(number) of iodine absorbed by 100 g of
fat or oil.
Significance
1. lodine number: directly proportional to
degree/content of unsaturated fatty acids.
2. Lower the iodine number ,less is the degree
of unsaturation
3. Iodine number is useful to analyze the
degree of adulteration.

1. ACID VALUE
Acid number : Lipases of bacterial origin are
responsible for rancidity & increase
content of free fatty acids of stored fat/oil.
Exposure to Moisture /water is
responsible for rancidity & increase
content of free fatty acids of stored fat /oil
Use: to detect rancidity. Acid number →
IODINE VALUE
directly proportional to rancidity (shelf life
/free fatty acids content of fat stored for FAT/OIL lodine number
longer duratión).
Coconut oil 7-10

2. SAPONIFICATION VALUE Butter 25-28

● Is the number of mg of KOH required to
neutralize the free acids and saponify Palm oil 45-55
the esters contained in 1.0 g of the Olive oil 80-85
substance.
● Aka: Koettsdorfer number/value Groundnut oil 85-100
SV= AV + EV
Cottonseed oil 100-110

3. ESTER VALUE Sunflower oil 125-135

● the number of mg of KOH required to
Linseed oil 175-200
saponify the esters in 1.0g of the
substance.
● If the Saponification Value and the Acid
value have been determined, the
difference between these two
represents the ESTER VALUE.
● (EV = SV - AV)