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Rajiv Gandhi university of Health Sciences , Karnataka
Department of Post-graduation studies,
Rasa shastra & Bhaishajya kalpana
COMPILATION ON TILA TAILA , ERANDA TAILA AND
SARSHAPA TAILA
Presenter
Dr.AKSHATA SWAMY
2nd
PG scholar
Under the guidance HOD
Dr Shankar gowda
Professor & HOD Dr Shankar gowda
Dept of PG studies RS&BK Dept of PG studies
TGAMC,Ballari TGAMC,Ballari
TARANATH GOVT AYURVEDIC MEDICAL COLLEGE,BALLARI
Contents
 Introduction
 Tila
 Tila taila
 Eranda
 Eranda taila
 Sarshapa
 Sarshapa taila
 Modern concept of oils and fats
 Bibliography
TILA
Latin Name : Sesamum indicum linn.
Family : Pedaliaceae
Classical names : Tila, pavitra, homadhanya, papaghna
Vernacular names :
English : Sesame, Gingelly.
Hindi : Til, Gingli.
Kannada : Ellu, Yallu.
Malayalam : Ellu, Schit-elu.
Marathi : Til, Tila.
Tamil : Ellu, Nal-lenny.
Telugu : Nuvvulu, Nuvvu.
Botanical Description
An erect branched or unbrached annular, 60-180 cm height, slightly foetid, sted soft
tomentose.
Leaves 7.5-12.5 cm. simple or variable, with upper ones narrowly oblong,
middle ones ovate and toothed and the lower ones lobate or pedatisect; small or big in
size being variable; lvs. Linear, oblong, lanceolate and in variable shape or kind, alternate
in general
Flowers white, pink or mauve-pink with darker markings, brine in racemes in the leaf-stalks;
Soft, hairy or glabrous; sub erect or drooping.
Fruits capsular, oblong-sub triangular, slightly compressed, dehiscent, deeply 4-
grooved, 1.5-5 cm. long. Seeds- black, brown or white, 2.5-3mm. long and 1.5mm.broad,
small; white and black in Colour, red also.
Ayurvedic properties :
Rasa : Madhura, Anurasa- Kashaya, Tikta.
Guna : Guru, Snigdha.
Virya : Ushna.
Vipaka : Madhura.
Dosha karma : Vata shamaka, Kapha-Pitta prakopaka, Tridosha shamaka when processed
with any other drug due to its ‘Yogavahi’ property.
Karma : Snehana, Sandhaniya, Keshya, Tvacchya, Balya, Vrana shodhana, Vrana ropana,
Dantya, Vrishya.
Uses : In Vatavyadhi, hair restorer, dermatopathy, dryness of the skin.
Others : There are three varieties of Tila but the Krishna tila is best in all.
Part used : Root, Leaf, Seed.
Chemical Composition :
Seeds contain various vitamins, particularly vitamin A, B and C. Seeds oil contains sesamin
and sesaminin and they also contain sesamol, a phenol compound. Analysis of a number of
samples of sesame seeds oil for glyceriote composition have led to conclusion that the
composition appears to be less affected by climatic and other factors during growth of the
crop. Sesame oil is rich in oleic and linoleic acids.Which together account for 85 percent of
the total fatty acids.
Pharmacological activities :
Antioxidant , Colesterolemic , Antioxidant, Hepato-protective, Antitumour, Hypotensive,
Nematicidal, Free radical scavenging activity, delta 5 desaturase inhibiting activity.
Substitutes and adulterants :
Sesamum oil is used as substitute and adulterant to Olive oil and Almond oil.
Formulation and preparation : Tiladi gudika, Tiladi lepa,Tilashtaka ,Tila bhallatkadi
TILA TAILA
Botanical Source : Til Taila consist of the oil extracted from the seeds of
Sesamum indicum.
Family : Pedaliaceae
Sanskrit : Tila Taila
Vernacular Names :
Hindi : Tila Tel, Krishna Tail, Metha Taila
Malayalam : Ellanna, Nallanna
Bengali : Kal Til
Gujarati : Tal nu Tel
Marati : Til Tail
Punjabi : Kunjad Tail
English : Sesam Oil, Gingelly Oil
Tamil : Nalenneya
Telugu : Manchinune
The word 'Taila' is derived from Sanskrit - "Tilodbhavam" means, one which is derived from
Tila- Sesamum. But in general,'Taila' is considered for all oils, specifically Tila Taila means
oil extracted from the seeds of Sesame indicum. Tila Taila (Sesame Oil) is an official oil
mentioned in British Pharmacopoeial Codex, British Pharmacopoeia and European
Pharmacopoeia.
Habit and Distribution Of Sesame Seeds :
It is largely cultivated throughout India being grown as an autum or even as a winter crop in
the warmer parts of the country, and as summer one in the colder areas.
Modern Review :
Sesame oil is the most stable vegetable oil, against oxidation .The oil is extracted from both
the varities of sesamum seeds ie black and white.
Description :
Sesame oil is a light yellow coloured with a pleasant odour of typical characterstic and bland
taste. Its density may vary between 0.916-0.920. It solidifies at –5 C and forms a buttery
mass. The sesame oil is soluble in ether, chloroform, petroleum ether and carbon disulphide
solution. It is partially soluble in alcohol and insoluble in water.
Chemical Composition :
Sesame oil is a mixture of oleine, stearine and other compounds of glycerine with acids of the
fatty series. The oil contains 1% sesamin and sesamolin. The latter breaks up into a phenolic
substance sesamol and sesamin. It also contains sesaminol, sesamolinol, - tocopherol,
phynoresinol . It contains saturated fatty acids like palmitic and non saturated fatty acids like
linoleic and oleic acid.
The Presence of the lignans imparts stability and protect the oil against oxidation.
It also contain an potent antioxidant principle 7-tocopherol. Hence oil penetrates the
tissue beneath the skin and neutralise oxygen radicals and encircles the blood stream
through the capillaries and act as the best natural conditioner for the skin by penetrating
the very marrow of the skin. On the way it gathers oil soluble toxins and takes them into
the blood stream to be eliminated by the body waste.Sesame oil also contains PUFA
(43%) which are supposed to be responsible for effect of the oil on blood pressure .Vit E,
Fat (57.99%) , Nitrogen(1.33%) are also components of sesame oil.
. It solidifies at C and forms a buttery mass. The sesame oil is soluble in ether,
chloroform, petroleum ether and carbon disulphide solution. It is partially soluble in
alcohol and insoluble inwater.
Rasapanchaka :
Rasa : Madhura
Anurasa : Tikta, Kashaya
Guna : Tikshna, Vyavayi, Sukshma, Ushna, Vishada, Guru, Sara,
Vikasi
Vipaka : Madhur
Doshaghnata : Vatakaphahara
Karma :
Brimhana / Lekhana, Prinana, Vrushya, Tvakprasadana, Mardavakara,
Sthairyakara, Balya, Garbhashaya shodhak, Bhagna sandhanakara, Medhavardhaka,
Keshya, Shulaprashamana, Ropaka, Vrana Nashak.
Therapeutic Activity :
Antibacterial, Antirviral, Anti-inflammatory, Antihepatatis, Anticancerous,
Antihypertensive, Antioxidant, Analgesic, Demulcent, Emollient, Emmengogue.
Pharmacologic Activity :
Antihypertensive effect and vascular disease prevention of sesamin were studied.
Dietary Sesame oil inhibits iron-induced oxidative stress.
In vitro Sesame seed oil has inhibited the growth of malignant melanoma.
Sesame seed oil has inhibited replication of human colon cancer cells.
Antioxidant and lipid peroxidation activity of sesame oil was also studied.
Adulterants :
Usually sesame oil is adulterated with cheap quality oil like Arachis oil, Cotton seed oil etc
ERANDA
Classical name : Eranda
Synonyms : Eranda ,Gandharvapatra , Panchangula , Vrdhamana , Uttanapatra , Chanchu ,
Vyaghripucchee , Vardhamana ,Vatari .
Vernacular name :
Hindi : Rendee
English : Castor
Kannada : Audala
Kula : Eranda kula
Family : Euphorbiaceae
Commercial name :Castor
Habitate : It grows all over India , mostly it is cultivated in the lands .
Morphology :
This is a tall glabcecous branched shrub or almost a small tree 2-4 meters or more high .the
stem and branches are green when young ,but turns grey .
Leaves : Alternate , long petioled ,stipulate , peltate , palmately compounded veined ,broad ,
nearly ,orbicular ,seven to ten or more lobed .Lobes membranes ablong linear ,acute or
acuminate gland serated .
Inflorence : Stout ,erect , sub –panicled racemes that terminate the main axis and branches.
Flowers : Fairly large , monocious , a petalous the staminate flowers are usually located in the
distal or upper half of the inflorescene in crowded manner ,and the pistillate at the basal part
.Occasionally a few pistillate flowers occur towards the top .
Fruit : A glabose or globular , oblong , explosively dehiscent three seeded capsule 1.2 to 2 cm
.Septicidally dehiscent into three two valued cocci .The fruit when young is green and usually
covered with short or long fleshy prickles .
Seed: Cornuculate oblong 1-1.5 cm long with smooth hard motted crustaceous testa and oily or
fleshy endosperm .
Varities –
I ) On the basis of the colour of the stem and inflorscence ,fruit spikes it is differentiated as
i) Rakta – Red (the leaves and fruits are rakta varna in colour )
ii) Shweta : white (Leaves and branches are shweta varna )
In variety it is classified as small and big varieties ,
II) On the basis of the life span of the plant it is classified as i) Bahuvarshayu ii)Varshayu
Official parts
Root ,Tender leaves ,Seed oil
Dose : Moola kalka : 10-20gm
Beeja – 2 to 6 grains
Taila – 4to 6ml
Properties of Eranda :
Rasa : Madhura , Katu , Kashaya
Guna : Guru , Snigdha ,picchila , teeksha , sookshma
Veerya : Ushna
Vipaka : Madhura
Doshghanata : Kaphavata shamaka
Rogaghnata : Mainly effective on samavata , Shothahara , Vedanasthapaka , Medya ,
Angamardaprashamana , Deepana , Bhedana , Krimighna , Saraka .
Chemical constituents :
Seeds contain 75% of kernel and 25% of hull ,Seeds weigh from 0.1 to 1 gm .Rich in phosphrous
.Hull is rich in mineral and also contains an alkaloid ricinine , resin , pigment etc.And also
several enzymes including lipase ,Maltage and invertase .The toxic principle ricin ,constituting
about 3% of the whole seeds is poisonous.
Sl.No Action Authentic books
Bp.N Md.N Dh.N Ch.S Su.S A.H
1 Samavata - - - + + +
2 Shothahara + + + + + +
3 Medya
4 Angamarda
prashamana
+ + + + + +
5 Deepana + + + + + +
6 Bhedana + + - + + +
7 Krimighna + + + + + +
8 Saraka + + + + + +
9 Kushta + + + + + +
10 Vedanasthapana + + + + + +
ERANDA TAILA
Castor oil is used for medicinal purpose to produce purgation to relieve pains and reduces
swelling etc .It is an efficient vatahara drug and so useful in many diseases.
Properties :
Rasa : Katu ,Madhura
Anurasa : Kashaya
Guna : Guru ,Snigdha , Sookshma , teekshna ,ushna ,picchila .
Doshghnata : Vatanashaka , Kaphavardhaka
Rogaghnata : Vatarakta ,Hridroga , Jeernajwara ,krimi ,Vridhiroga , Kushta
Oil of red variety of castor seeds is still more penetrating , hot in potency and sticky and has a
bad smell .
Eranda taila shreshtata :
Among all the tailas Eranda taila is sreshta for virechana .
Dose : 4-16ml
Anupana : Yoosha or Ushna jala
Clinical and experimental studies :
A study “ Castor oil an update on mechanism of action ’’ castor oil expressed from the seeds of
ricinus communis is an effective laxative .The mechanism by which castor oil produces its effect
on gutt could involve inhibition of Na++
-ATPase , activation of adenylate cyclase , stimulation of
prostaglandins and nitric oxide bio-synthesis .Castor oil changes the intestinal permeability and
causes historical abnormalities , but these alteration are not essential for the laxative effect
.Platelate activating factor (PAF) is most likely one of the mediation of the castor oil induced
damage ,while nitric oxide has a protective role possibly by reducing PAF bio-synthesis .
Modern view :
Castor oil
Biological source : Castor oil is the fixed oil obtained by the cold expression of the seeds of
ricinus communis.
Geographical sources : Castor seeds are produced in almost all tropical and subtropical
countries .In India ,Castor is one of the major oil seed crops ,and India is the second largest
producer of castor seeds in the world , producing about 2,80,000 tonnes per annum .Brazil
,USSR ,Thailand ,USA and Rumania are the other countries producing the drug on the large
scale .In India it is largely grown in the Andhrapradesh ,Gujrat ,and Karnataka .
Preparation of castor oil :
Castor oil can be prepared by two different methods , the first being the crushing of whole or
decorticated seeds in power driven hydraulic presses and the second one known as Ghani ,which
consists of manually operated screw press driven by bullocks .For commercial scale of extraction
,the first method is adopted .The oil thus produced is a non-medicinal castor oil.
The seeds are greeded and made freeof impurities like metallic pieces of iron & sand .The seeds
are decorticated and hulls are removed .If the seeds are not decorticated ,the manorial value of
the cake increases .But for medicinal purposes it is desired that the seeds should be corticated ,as
it improves the colour of the oil and also helps in controlling the acid value of the oil.
Decorticated seeds are pressed under hydraulic press with a pressure of 2 tonnes per square
inch which helps in extracting out 30% of the oil present in the seeds at room temperature .The
oil is known as cold drawn oil .Rest of the oil from the seeds is removed by further increasing the
pressure ,and sometimes by hot pressing or even by solvent extraction process.The oil thus
processed is not suitable for medicinal purposes .The cold drawn oil is then steamed at 800
C to
destroy the enzyme lypase and ricin .It is then bleached and de-acidified with sodium
bicarbonate to remove the mucilaginous matter present in the oil.Finally it is treated with
activated earth or animal charcoal to remove the impurities adsorption and filled into the
containers.
Organoleptic characters
Colour – Pale yellow
Odour –Nauseating
Taste – First it bland but afterwards slightly acrid and usually nauseating .It is viscous and
transparent liquid .
Identification :
1. It mixes with half its volume of light petroleum ether (400
to 600
C)
2. Add to the oil equal volume of alcohol ; clear liquid is obtained .On cooling at 00
C and
on storage for three hours ; the liquid remains clear.
Solubility :
It is soluble in alcohol (an exception to the category of fixed oils); miscible in chloroform
,solvent ether ,glacial acetic acid and petroleum ether .It is soluble in mineral oil.
Chemical constituents
Castor oil chiefly contains triglyceride of ricinoleic acid (about 80%) other glyceroids are also
present in the drug , where the fatty acids are represented by icoricinoleic ,linoleic ,stearic and
isostearic acids.The viscocity of the castor oil is due to the riceleic acid .
Ricinoleic acid : CH3(CH2)5CHOHCH2CH =CH(CH2)7CHOOH
Standards
1.Weight per ml – 0.945 to 0.965
2. Acid value – not more than 2
3. Acetyl value – not less than 143
4.Iodine value – 82- 90
5. Saponification value – 177 -185
6.Hydroxyl value- 161 – 168
7. Optical rotation - not less than + 3.50
8.Ignition temperature -449 0
C
9.Density – 1.473 to 1.477
10.Solidifying point – 10 to 18 0
C
11.Viscocity -8 to 0 pieces
12.Refractive index – 1.473-1.477
13.Surface tension at 200
C – 39 dynes/cm
14.Specific rotation - +0.961 to 0.963
Uses
 Castor oil is used as catheratic
 It is also used for lubrication commercially
 Several other forms of castor oil such as dehydrated castor oil (DCO) or hydrated castor
oil are used industrially several other purposes .
 The catheratic property of the castor oil is due to irritant action of the ricinoleic acid.
 Castor oil is often given orally or as aromatic castor oil or in the form of capsules.
Therapeutic uses :
 It is used in abortificient paste and ricinoleic acid is used in contraceptive jellies.
 Atropine and cocaine for ophthalmic purposes are suspended in castor oil
 It is also used as an emollient in the preparation of lip-stick and as sulphoresinolate in
tooth formulation being strong bacteriocide.
 Other cosmetic purposes for which the oil is used includes the perfumed hair oil and hair
fixers.
 Castor cake is used as a source of enzyme lipase.
Sl.No Diseases Authentic books
Ch.S Su.S A.H Bp.N SNGN Dh.N MpN YR
1 Gulma + + + + + + + +
2 Vatarakta + + - + - + + -
3 Hridroga + + + + + + + -
4 Jeernajwara + - - - - + + -
5 Krimi + + + + + + + +
6 Kushta - + - + - - - +
7 Vishamajwara - + + + - - + +
8 Vriddhiroga - + + + + + - +
SARSHAPA
Latin name - Brassica campesatris
Family - Cruciferae
Vernacular name
Hindi : Sarson
English : Musterd
Kannada : Sasive
Synonyms - Katu sneha, Tantubh, sarshap
Rasa panchaka
Rasa : Katu, tikta
Guna : Tikshna, Ruksha (leaves ) , Snigdha (Taila, Beej)
Virya : Ushna
Vipaka : Katu
Doshaghnta - Kapha – vata shamak, Pitta vardhak
Parts used – Beeja , Taila
Chemical composition
Mustard oil is extracted at low pressure at low temperature (40-60oc). The main chemical
component of mustard oil is allyl iso thiocynate and it has 30% protein, calcium, phytins,
phenolies and natural antioxidants. And it contains high amount of unsaturated fatty acids and
good ratio of polyunsaturated fatty acids which is good for heart. Oil is a skin and mucous
membrane irritant.
Fatty acids composition of mustard oil;-
Fatty acid Range
1. Palmitic acid 1-3%
2. Stearic acid 0.4 - 3.5 %
3. Arachidic acid 0.5-2.4%
4. Lignoceric acid 0.5-1.1%
5. Oliec acid 12-24%
6. Erucic acid 40-55%
7. Linolenic acid 7-10%
Physical properties;-
Refractive index (at 20oC) 1.470 – 1.474
Viscosity (at 20oC) - CPZ 74-120
Solidification temperature 8 to 10oc
Solubility soluble in benzene , petroleum ether,
acetone.
Colour - yellow
Smell - specific
Transparence - Transparent
Moisture content - 0.15 – 0.4%
Saponification value - 170 –180
Iodine value - 92 –107
Tocopherol content 31.8 mg%
Non saponifiable matters 1-3%
Pharmacological & therapeutical uses:-
It has Lekhana , Kusthaghna , jantughna ,vednasthapak and Sneha properties . And its oil is a
skin and mucous membrane irritant.it is good for heart. Glucinolate, the pungent principle in
musterd oil, has antibacterial, antifungal, and anti-carcinogenic properties.
SARSHAPA TAILA
Sarshapa taila is pungent , hot in potency , penetrating deep into the tissues , mitigates kapha ,
semen , vata , easily digestable ,produces bleeding diseases , rashes on the skin , leprosy and
other diseases , haemorrhoids , ulcers and worms .
Biological source :
In India several varities of mustard are available which differ from each other in their
morphological characters and biological origin .Black mustard is used medicinally , while all
other are important as a source of fixed oil and as condiments.
Following are a few commercially important species of mustard
Types of Species :
1.Black mustard – Brassica nigra linn
2.Gray mustard – Brassica juncea linn
3.Indian rape (Toria) – Brassica compestris
4.Rape seed – Brassica compestris
5.White mustard – Brassica alba
Black mustard oil :
It is fixed oil obtained from well mustard seeds of Brassica nigra or brassica juncea
Method of preparation
The oil is prepared from expression
Organoleptic characters :
Colour -Yellowish
Odour – Disagreeable
Appearance – Slight viscous
Opalesence – Transparent
Clarity – Clear
Properties of Sarshapa
Rasa : Katu
Guna : Ushna , Laghu , Snigdha ,Teekshna
Virya : Ushna
Vipaka : Katu
Doshghna : Kaphanashaka , Vatanashaka
Chemical constituents : Mustard oil contains glyseroids of arachidic (0.5%) Behenic (2-3%) ,
Eicosenoic acid (7-8%) , Erusic acid (40-60%) , Lignoceric acid (1-2%) , Linoleic acid (14-18%)
, Linolenic acid (6.5 – 7%) , Oleic acid (20-22%) , Myristic acid (0.5 – 10 %) .
Specific standards :
Specific gravity : 0.914 – 0.923
Unsaponifiable matter – 0.9-1%
Refractive index – 1.472-1.4733
Solidifying point – 11 to 170
C
Iodine value – 96-124
Saponification value – 173- 184
Uses of Mustard oil :
Fixed oil is used as edible oil after refining
It is also used as condiment and im manufacture of soap .
Refined mustard oil is used in vegetable ghee.
Medicinal properties are due to allyl isothiocynate which is local irritant and emetic ,if applied
externally.
Therapeutic uses
Sl.No Diseases Authentic books
Ch.S Su.S SNGN Bp.N HS A.H YR Md.N
1 Kusta + + + + + - + +
2 Krimi - + - + + - + +
3 Arsha - - - + - + - -
4 Grahi - - - - + - - +
5 Medhanashaka - - + - + + + -
Modern Concept of Oils and Fats
Oils and fats are products from vegetable, animal, marine and mineral sources. Oils are liquid at
20°C and fats are in solid state at normal temperature. Natural fats are glycerides of saturated
fatty acid or long chain fatty acid for which it is solid and oils are glycerides of unsaturated fatty
acid or short chain glyceride for which it is liquid. The two terms are purely conventional since
the same substance may be a fat in one climate and oil in another. Thus ghee is a fat in winter
and oil in summer. Chemically fats contain more saturated ( i.e. palmitic and stearic ) fatty acids
therefore it is hard and melts at higher temperature and oils contain large proportion of
unsaturated fatty acid (i.e. oleic) hence it is liquid and melts at lower temperature. The short and
medium chain fatty acids are liquids while long chain fatty acids are solids. The high melting
point is due to the close packing of the straight chain fatty acid molecules. The solubility in water
decreases while melting point and boiling point increases with increase in chain length.
Comparison of fats and oils are given in the Table - 23
Table – 23 , Comparison of fats and oils
Fat Oil
1.Solid 1.Liquid
2. Contains more saturated fatty acids( i.e.
palmitic and stearic )
2. Contains more unsaturated fatty acids ( i.e.
Oleic acid )
3. Solid due to more saturated fatty acids 3. Liquid due to more unsaturated
fatty acids
4. Melts at higher temperature due
to more saturated fatty acids
4. Melts at lower temperature due to more un
saturated fatty acids
5. Found in animals and plants 5. Found in plants eg. Mustard oil, sesame oil,
castor oil, ground nut oil etc.
Comparison of unsaturated and saturated fat are given in Table - 24
Unsaturated Fat Saturated Fat
1. It is the fat that the acid radical of
which is capable of entering into direct
combination with hydrogen and with certain
other substances to make saturated compounds.
1. Cannot react in direct combination
with other substances.
2. One or more pairs of carbon atoms in the
fatty acid radical or radicals are combined with
double bonds. At these points addition of
hydrogen or other atoms may make a saturated
compound.
2. All the carbon atoms in the fatty
acid radicals are combined with each
other by single bonds.
3. These are liquid. 3. These are solid.
4. More active chemically which has
physiology significance.
4. Lesser active.
Table .No.25 Classification of Oils and Fats
Oil
Animal Vegetable
Marine e.g.
Shark liver oil
Cod liver oil
Margarine
Terrestrial
e.g.
Sheep foot oil
Horse foot oil
Egg yolk
lard oil
Drying oils
e.g.
Linseed oil
Poppyseed oil
Semi drying e.g. Sesame
oil
Mustard oil, Croton oil,
Corn oil, Soyabeen oil
Non drying
e.g. Castor oil
Almond oil
Arachis oil
peanut oil
Olive oil
Iodine value of Drying oil - 130 - 200
Iodine value of Semi drying oil - 95-130
Iodine value of Non drying oil Less than 95
Fats
Animals Vegetable
Ghee Butter hard Coconut oil, palm oil
Coco Butter
Physical properties of oils and fats
1. Fats and oils are solids or liquids having no colour or taste in pure state.
2. They are lighter and insoluble in water and therefore form the upper layer when mixed with it.
3. They are freely soluble in organic solvents like their acetone, alcohol, benzene, chloroform etc
called fat solvents.
4. They readily form emulsions when mixed with water in the presence of soap, gelatin or other
emulsifier.
FUNCTIONS OF LIPIDS
The lipids serve the following important functions :
1. Storage form of energy (Triglycerides)
2. Structural components of bio-membranes (phospholipids and cholesterol).
3. Some deposits of lipids may exert an insulating effect in the body, lipids around internal
organs like kidney etc. may provide padding and protect the organs.
4. Lipids supply Essential fatty acid (EFA), which cannot be synthesized in the body and are
essential in the diet for normal health and growth.
5. Give shape and contour to the body.
6. Metabolic regulators (steroid, hormones and prostaglandin).
7. Acts as surfactants, detergents and emulsifying agents (amphipathic lipids).
8. Act as electric insulators in neurons.
9. Helps in absorption of fat soluble vitamins (A, D, E and K).
10. Adds taste and palatability to food.
Table – 26 , COMPOSITION OF OILS AND FATS
Name of fatty
Acid
Saturated fatty
acids (%)
MUFA (%) PUFA (%)
Coconut oil 86x 12 02
Groundnut oil 18 46 36
Gingelly oil 13 50 37
Palm oil 42 52 06
Corn oil 13 25 62
Cotton Seed oil 26 19 55
Sesame oil 12 48 40
Mustard oil 34xx 48 18
Safflower oil 09 12 79
Sunflower oil 12 24 64
Butter 75 20 05
Ox (Tallow) 53 42 05
Pig (Lard) 42 46 12
Fish oil 30 13 57
X Saturated fatty acids are medium chain fatty acids.
Xx Contains erucic acid, 22c, 1 double bond
DIGESTION OF LIPIDS :
Dietary lipids are emulsified by the peristaltic movements. The lingual lipase (optimum pH 2.5 -
6) from the mouth enters stomach and acts on short chain triglycerides (SCT) which are present
in milk, butter, ghee, coconut oil. Gastric lipase (optimum pH about 5.4) which is acid stable is
secreted by gastrin upto 30% digestion of triglycerides occurs in stomach. The pancreatic lipase,
cholesterol esterase and phospholipase A2, Bile salts are important in the digestion of lipids. The
bile salts present in the bile (sodium glucocholate and sodium taurocholate) have lower surface
tension and thus helps in emulsification of fat droplets in the intestine.
ABSORPTION OF LIPIDS :
Glycerol as well as small chain and medium chain fatty acids (chain length less than 14 carbons)
are directly absorbed from the intestinal lumen, into the portal vein and taken to the liver, and are
immediately utilized for energy. Long chain fatty acids (chain length more than 14 carbons) are
absorbed by forming micelle with the help of bile salts). The theory proposed by Bergstron
which won Nobel prize in 1982. Lipids are amphipathic in nature as it contains a hydrophobic
tail and hydrophilic head. Amphipathic lipids gets oriented at oil water interfaces with the polar
groups in the water phase and the non polar groups in the oil phase. When a critical
concentration of these amphipathic lipids are present in an aqueous medium, they form Micelles.
Micelle formation, facilitated by bile salts, is the prerequisite for fat digestion and absorption
from the intestine. The driving force for micelle formation is hydrophobic since the tail groups
cannot break the hydrogen bonds between water molecules and as a result cluster together in
close proximity.
The products of digestion, namely 2-monoglycerides, long chain fatty
acids, cholesterol, phospholipids and lysophospholipids are incorporated into
molecular aggregates to form mixed micelle. The micellization helps in dispersing the fatty acid
molecules in the aqueous medium of intestinal lumen.
In this micellar form, the products of digestion of dietary lipids are
presented for absorption at the microvillous surface of jejunal mucosa.
Inside the intestinal mucosal cell, the long chain fatty acid (LCFA) are re esterified to
form triglyceride.
Short chain fatty acids (SCFA) seen in ghee butter etc and middle chain fatty acids
(MCFA) seen in coconut oil do not need re-esterification and directly enter into blood vessels
SCFA and MCFA are better absorbed than LCFA.
Table – 27 , Differences in metabolisms of SCFA and LCFA containing Triglycerides.
SCFA and MCFA LCFA
1 Examples Butyric acid (c=4)
in butter and lauric acid (c=12)
in
coconut oil
Palmitic acid (C=16)
and stearic acid (C=18)
in vegetable oils and
animal fats.
2 Digestion in
stomach
Hydrolysed Not hydrolysed
3 Pancreatic lipase Not necessary Essential
4 Bile salts Not necessary Absolute essential
5 Inside intestinal
cells
TAG is hydrolysed
to form fatty acids
Free fatty acids are re
esterified to form TAG
6 Absorbed to Directly to blood To lymphatics, then to
thoracic duct
7 Absorbed as FFA carried by
albumin
TAG, carried by
chylomicrons
8 Immediate fate Oxidised by
peripheral cells
Deposited in the
adipose tissue
9 Carnitine Is not required for
oxidation
Is required for
Oxidation
10 Clinical
application
No effect on
artherosclerosis
Leads to
hypercholesterolemia
and arteriosclerosis
Lipotropic agents :
Lipotropic factors are agents which are required for the normal mobilization of fat from
liver thus preventing accumulation of fat in liver cells. This phenomenon itself is called
lipotropism.
Choline, Lecithin, Methionine, Betaine, Inositol etc are lipotropic agents.
Casein is also a lipotropic agent, probably due to high content of methionine. Lecithin
(phosphatidylcholine is abundant in seeds and sprouts)
Lecithin has the capacity to lower the surface tension of water and acid in the
emulsification and helps in the formation of lipid water mixture.
DEGRADATION OF OILS AND FATS / RANCIDITY :
Oils and fats tend to spoil on storage due to the production of free fatty acid and by lipase
activity or other hydrolytic activity. On storage those changes produce unpleasant taste and
odour which is termed as Rancidity of oils and fats.
Five factors contribute to the oxidative deterioration of fats and oils.
(1) Oxygen or air
(2) Heat
(3) Light
(4) Pro-oxidant metals
(5) Time
ROUTES TO RANCIDITY :
Major routes to oil / fats rancidity are :
(1) Hydrolysis
(2) Oxidation
(3) High temperature polymerization
(1) Hydrolysis :
Hydrolytic rancidity is due to partial hydrolysis of triacyl glycerol
molecular due to traces of hydrolytic enzymes present in naturally occurring fats
and oils.
Triacyl glycerol Diacyl glycerol Monoacylglycerol
Water Fatty acid Water Fatty acid .
Fatty acid +
Glycerol
Hydrolysis is a major problem with short chained fatty acid triglycerides such as lauric
acids. Fat degradation reaction of fats and oils with water occurs in triglyceride fraction and is
manifested by the formation of free fatty acid.
The principles involved in presenting the hydrolytic reaction of fats and
oils are
(1) Avoidance of water by all possible means.
(2) Knowledge and understanding of water can be introduced into a particular system.
It should be understood that all fats and oils exhibit a degree of solubility in water, and as
a rule of thumb can contain about 0.1% moisture at 20°C. Solubility of water in oil will increase
with temperature and decrease as the average chain length of the components fatty acids
increase.
Sometimes hydrolysis of water with non triglyceride portion occurs which are
troublesome or produce undesirable sludge / precipitate and which in extreme cases tends to
microbial fermentations which in turn results in enzymatic hydrolysis. This is not a major
concern to oils and fats unless the presence of free fatty acid and moisture could lead to increase
solubilization of metallic components of the equipment.
(2) OXIDATION :
Oxidation rancidity is the result of partial oxidation of unsaturated fatty acid with resultant
formation of epoxides and peroxides of small molecular weight fatty acid by peroxides and free
radical. Oxidation causes off flavor instability and primary focus of most analysis. The degree of
oxidation of fats and oil is determined by analyzing the artifacts formed. These may be divided
into two classes viz primary and secondary. Primary oxidation products are those which are
formed initially from the reaction of oxygen, free radicals and fats. These are unstable and
decompose to form secondary reaction product.
Oxidation occurring in processed oils are mainly due to -
1. Auto-xidation
2. Photo-oxidation
3. Enzymatic oxidation
1. Auto-oxidation :
Auto-oxidation are the process through which free radicals are formed by the loss of hydrogen
atom from methylene group adjacent to a double bond. This is supposed to be initiated by light
heat etc. Through this free radical chain reaction involving initiation, propagation and
termination occurs.
R'CH2CH = ChCH2R" R' CH CH = CH CH2 R"
heat, metals, O2
Atmosphere oxidation converts this free radicals into peroxide which is
also a free radical.
R' CH2 CH = CH CH2R" + O2 R' CH CH = CH CH2 R"
00 - X
The peroxide radical again reacts with another molecule of the original oxidisable substance to
produce a hydro-peroxide, another free radical.
R'CH CH = CH CH2 R" + R' CH CH = CH CH2 R"
00-X 00H
R' CH CH = CH CH2 " + R' CHC = CH CH2 R"
Such a long chain reaction provides and ultimately the hydro-peroxide decomposed to produce
the undesirable aldehydes and esters.
The overall preponderance of oxidation reaction of fats and oils is related to fatty acid
composition and more specifically to the type and amount of unsaturation. Thus oils and fats
with higher degree of unsaturation or higher iodine value will peak up oxidative rancidity earlier.
Initially oxidation of fats is usually slow, but once the peroxide formation reaches a certain level
the rates of oxidation increases and fat soon begins to give rancid taste and odour.
2. Photo-xidation
Photoxidation is much faster reaction that catalyzes the attack at the double bond by singlet
oxygen formation and may initiate the slower auto-oxidative reaction by formation of trace
amounts of hydro-peroxides made possible by pigments (chlorophyll) in the finished oil.
3. Enzymatic oxidation
The most important classes of enzymes causing lipid oxidation are lipoxygenase. These
enzymes are quite common in the plant world and thus are present in all of the vegetable oil
seeds . Lipoxygenase only acts on the polyunsaturated fatty acids and catalyzes the addition of
oxygen to the alpha-methylene carbon, creating hydro=peroxides, similar to those found during
autoxidation. These enzymes do not survive processing because of their destruction by heat.
Hence inorder to avoid enzymatic oxygen the oil should be heated to temperature for the
complete removal of moisture .
Tests of Rancidity :
Following are the tests to check the rancidity in oil and fat.
1. Measurement of acid value / free fatty acid
2. Peroxide value
3. Colorimetric method
4. Kreis method
5. Para anisidin test
6. Thiobarbituric acid number.
STABILISATION OF OILS / FATS :
Methods available to protect fats and oils against oxidative deterioration
during the unit processing operations are as follows :
1. Use of adequate temperature processing and storage.
2. Use of inert gas blanketing during storage.
3. Avoidance of light.
4. Avoidance of prooxidants e.g. metals like copper, lead.
Antioxidants can be used as preventive measure against rancidity and
have shelf life can be enhanced.
Bibliography
1. Agnivesha. Charaka Samhita. Redacted by Charaka and Dridhabala with Ayurveda
Deepika Commentary by Chakrapanidatta and Vidyotini Hindi Commentary by
Pt.Kashinath Shasthri.Varanasi: Chaukambha bharati academy; 2009.reprint
2. Vagbhatacharya, Ashtangahridayam with commentaries of Sarvangasundara of
Arunadatta and Ayurveda Rasayana of Hemadri, Annoted by Dr.Annamoreshwar kumte
and Krishna ramachandra shastrinoure edited by Pt.Harisadashiva shastry
Paaradakarabhishagaacharya, Varanasi, Choukhambasuarabharati prakashana, reprint
2010.
3. Vriddha Vaghbhatacharya , Ashtanga Sangraha , Induvirachita ‘ Shashilekha’
commentary edited by Dr. Shivaparsad sharma , 1st
edition ,Varanasi ; Chaukhambha
Sanskrit series office.
4. Sushruta , Susharuta samhita ShriDalhanacharya virachita and Nyayachandrikapanjika of
shriGayadasacharya on nidanasthana, with the Nibandhasangraha commentary edited by
vaidya Yadavjitrikamjiacharya,Varanasi, choukhambasurabharati prakashan, reprint
2012.
5. Bhavaprakasha Bhavamishra ,Bhavaprakash edited with The vidyotini hindi commentary
By Sri Brahamasankara Mishra , and Rupalalji vaisya ,8th
edition ,Varanasi;
Chaukhambha Sanskrit sansthan ,1998, Purvardha
6. Sri Chakrapanidatta. Chakradatta with Vaidyaprakasha Hindi commentary. by
Dr.Indradev Tripathi.edited by Prof.Ramanath Dwivedy. Varanasi: Chaukhamba Sanskrit
Bhawan; Reprint- 2010
7. Kaviraj Shri Govindadassen, Bhaishajya Ratnavali. edited with Siddiprada Hindi
commentary, by Prof. Siddhinandan Mishra, Varanasi, Published by Chaukhamba
surbharti prakashan, reprint 2015,chapter 5
8. Ananymous. Yogarathnakar vidyotini hindi tika sahit, edited by Bhisaga Ratna Bhramha
Shankar Sastri. 6th
edition,Varanasi: Choukambha prakashana ,Reprint 2015
9. P.C.sharma,M.B.Yelne,T.J.Dennis.Database on medicinal plants used in Ayurveda &
siddha.CCRAS:New Delhi;Reprint 2005.
10. D.M. Vasudevan, S. Sreekumari- ' Text Book of Biochemistry for medical students 3rd
edition, New Delhi ;Jaypee Brothers, Medical Publishers (P) Ltd

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Compilation on tila ,sarshapa, n eranda taila pdf

  • 1. Rajiv Gandhi university of Health Sciences , Karnataka Department of Post-graduation studies, Rasa shastra & Bhaishajya kalpana COMPILATION ON TILA TAILA , ERANDA TAILA AND SARSHAPA TAILA Presenter Dr.AKSHATA SWAMY 2nd PG scholar Under the guidance HOD Dr Shankar gowda Professor & HOD Dr Shankar gowda Dept of PG studies RS&BK Dept of PG studies TGAMC,Ballari TGAMC,Ballari TARANATH GOVT AYURVEDIC MEDICAL COLLEGE,BALLARI
  • 2. Contents  Introduction  Tila  Tila taila  Eranda  Eranda taila  Sarshapa  Sarshapa taila  Modern concept of oils and fats  Bibliography
  • 3. TILA Latin Name : Sesamum indicum linn. Family : Pedaliaceae Classical names : Tila, pavitra, homadhanya, papaghna Vernacular names : English : Sesame, Gingelly. Hindi : Til, Gingli. Kannada : Ellu, Yallu. Malayalam : Ellu, Schit-elu. Marathi : Til, Tila. Tamil : Ellu, Nal-lenny. Telugu : Nuvvulu, Nuvvu. Botanical Description An erect branched or unbrached annular, 60-180 cm height, slightly foetid, sted soft tomentose. Leaves 7.5-12.5 cm. simple or variable, with upper ones narrowly oblong, middle ones ovate and toothed and the lower ones lobate or pedatisect; small or big in size being variable; lvs. Linear, oblong, lanceolate and in variable shape or kind, alternate in general Flowers white, pink or mauve-pink with darker markings, brine in racemes in the leaf-stalks; Soft, hairy or glabrous; sub erect or drooping. Fruits capsular, oblong-sub triangular, slightly compressed, dehiscent, deeply 4- grooved, 1.5-5 cm. long. Seeds- black, brown or white, 2.5-3mm. long and 1.5mm.broad, small; white and black in Colour, red also.
  • 4. Ayurvedic properties : Rasa : Madhura, Anurasa- Kashaya, Tikta. Guna : Guru, Snigdha. Virya : Ushna. Vipaka : Madhura. Dosha karma : Vata shamaka, Kapha-Pitta prakopaka, Tridosha shamaka when processed with any other drug due to its ‘Yogavahi’ property. Karma : Snehana, Sandhaniya, Keshya, Tvacchya, Balya, Vrana shodhana, Vrana ropana, Dantya, Vrishya. Uses : In Vatavyadhi, hair restorer, dermatopathy, dryness of the skin. Others : There are three varieties of Tila but the Krishna tila is best in all. Part used : Root, Leaf, Seed. Chemical Composition : Seeds contain various vitamins, particularly vitamin A, B and C. Seeds oil contains sesamin and sesaminin and they also contain sesamol, a phenol compound. Analysis of a number of samples of sesame seeds oil for glyceriote composition have led to conclusion that the composition appears to be less affected by climatic and other factors during growth of the crop. Sesame oil is rich in oleic and linoleic acids.Which together account for 85 percent of the total fatty acids. Pharmacological activities : Antioxidant , Colesterolemic , Antioxidant, Hepato-protective, Antitumour, Hypotensive, Nematicidal, Free radical scavenging activity, delta 5 desaturase inhibiting activity. Substitutes and adulterants : Sesamum oil is used as substitute and adulterant to Olive oil and Almond oil. Formulation and preparation : Tiladi gudika, Tiladi lepa,Tilashtaka ,Tila bhallatkadi
  • 5. TILA TAILA Botanical Source : Til Taila consist of the oil extracted from the seeds of Sesamum indicum. Family : Pedaliaceae Sanskrit : Tila Taila Vernacular Names : Hindi : Tila Tel, Krishna Tail, Metha Taila Malayalam : Ellanna, Nallanna Bengali : Kal Til Gujarati : Tal nu Tel Marati : Til Tail Punjabi : Kunjad Tail English : Sesam Oil, Gingelly Oil Tamil : Nalenneya Telugu : Manchinune The word 'Taila' is derived from Sanskrit - "Tilodbhavam" means, one which is derived from Tila- Sesamum. But in general,'Taila' is considered for all oils, specifically Tila Taila means oil extracted from the seeds of Sesame indicum. Tila Taila (Sesame Oil) is an official oil mentioned in British Pharmacopoeial Codex, British Pharmacopoeia and European Pharmacopoeia. Habit and Distribution Of Sesame Seeds : It is largely cultivated throughout India being grown as an autum or even as a winter crop in the warmer parts of the country, and as summer one in the colder areas.
  • 6. Modern Review : Sesame oil is the most stable vegetable oil, against oxidation .The oil is extracted from both the varities of sesamum seeds ie black and white. Description : Sesame oil is a light yellow coloured with a pleasant odour of typical characterstic and bland taste. Its density may vary between 0.916-0.920. It solidifies at –5 C and forms a buttery mass. The sesame oil is soluble in ether, chloroform, petroleum ether and carbon disulphide solution. It is partially soluble in alcohol and insoluble in water. Chemical Composition : Sesame oil is a mixture of oleine, stearine and other compounds of glycerine with acids of the fatty series. The oil contains 1% sesamin and sesamolin. The latter breaks up into a phenolic substance sesamol and sesamin. It also contains sesaminol, sesamolinol, - tocopherol, phynoresinol . It contains saturated fatty acids like palmitic and non saturated fatty acids like linoleic and oleic acid. The Presence of the lignans imparts stability and protect the oil against oxidation. It also contain an potent antioxidant principle 7-tocopherol. Hence oil penetrates the tissue beneath the skin and neutralise oxygen radicals and encircles the blood stream through the capillaries and act as the best natural conditioner for the skin by penetrating the very marrow of the skin. On the way it gathers oil soluble toxins and takes them into the blood stream to be eliminated by the body waste.Sesame oil also contains PUFA (43%) which are supposed to be responsible for effect of the oil on blood pressure .Vit E, Fat (57.99%) , Nitrogen(1.33%) are also components of sesame oil. . It solidifies at C and forms a buttery mass. The sesame oil is soluble in ether, chloroform, petroleum ether and carbon disulphide solution. It is partially soluble in alcohol and insoluble inwater.
  • 7. Rasapanchaka : Rasa : Madhura Anurasa : Tikta, Kashaya Guna : Tikshna, Vyavayi, Sukshma, Ushna, Vishada, Guru, Sara, Vikasi Vipaka : Madhur Doshaghnata : Vatakaphahara Karma : Brimhana / Lekhana, Prinana, Vrushya, Tvakprasadana, Mardavakara, Sthairyakara, Balya, Garbhashaya shodhak, Bhagna sandhanakara, Medhavardhaka, Keshya, Shulaprashamana, Ropaka, Vrana Nashak. Therapeutic Activity : Antibacterial, Antirviral, Anti-inflammatory, Antihepatatis, Anticancerous, Antihypertensive, Antioxidant, Analgesic, Demulcent, Emollient, Emmengogue. Pharmacologic Activity : Antihypertensive effect and vascular disease prevention of sesamin were studied. Dietary Sesame oil inhibits iron-induced oxidative stress. In vitro Sesame seed oil has inhibited the growth of malignant melanoma. Sesame seed oil has inhibited replication of human colon cancer cells. Antioxidant and lipid peroxidation activity of sesame oil was also studied. Adulterants : Usually sesame oil is adulterated with cheap quality oil like Arachis oil, Cotton seed oil etc
  • 8. ERANDA Classical name : Eranda Synonyms : Eranda ,Gandharvapatra , Panchangula , Vrdhamana , Uttanapatra , Chanchu , Vyaghripucchee , Vardhamana ,Vatari . Vernacular name : Hindi : Rendee English : Castor Kannada : Audala Kula : Eranda kula Family : Euphorbiaceae Commercial name :Castor Habitate : It grows all over India , mostly it is cultivated in the lands . Morphology : This is a tall glabcecous branched shrub or almost a small tree 2-4 meters or more high .the stem and branches are green when young ,but turns grey . Leaves : Alternate , long petioled ,stipulate , peltate , palmately compounded veined ,broad , nearly ,orbicular ,seven to ten or more lobed .Lobes membranes ablong linear ,acute or acuminate gland serated .
  • 9. Inflorence : Stout ,erect , sub –panicled racemes that terminate the main axis and branches. Flowers : Fairly large , monocious , a petalous the staminate flowers are usually located in the distal or upper half of the inflorescene in crowded manner ,and the pistillate at the basal part .Occasionally a few pistillate flowers occur towards the top . Fruit : A glabose or globular , oblong , explosively dehiscent three seeded capsule 1.2 to 2 cm .Septicidally dehiscent into three two valued cocci .The fruit when young is green and usually covered with short or long fleshy prickles . Seed: Cornuculate oblong 1-1.5 cm long with smooth hard motted crustaceous testa and oily or fleshy endosperm . Varities – I ) On the basis of the colour of the stem and inflorscence ,fruit spikes it is differentiated as i) Rakta – Red (the leaves and fruits are rakta varna in colour ) ii) Shweta : white (Leaves and branches are shweta varna ) In variety it is classified as small and big varieties , II) On the basis of the life span of the plant it is classified as i) Bahuvarshayu ii)Varshayu Official parts Root ,Tender leaves ,Seed oil Dose : Moola kalka : 10-20gm Beeja – 2 to 6 grains
  • 10. Taila – 4to 6ml Properties of Eranda : Rasa : Madhura , Katu , Kashaya Guna : Guru , Snigdha ,picchila , teeksha , sookshma Veerya : Ushna Vipaka : Madhura Doshghanata : Kaphavata shamaka Rogaghnata : Mainly effective on samavata , Shothahara , Vedanasthapaka , Medya , Angamardaprashamana , Deepana , Bhedana , Krimighna , Saraka . Chemical constituents : Seeds contain 75% of kernel and 25% of hull ,Seeds weigh from 0.1 to 1 gm .Rich in phosphrous .Hull is rich in mineral and also contains an alkaloid ricinine , resin , pigment etc.And also several enzymes including lipase ,Maltage and invertase .The toxic principle ricin ,constituting about 3% of the whole seeds is poisonous. Sl.No Action Authentic books Bp.N Md.N Dh.N Ch.S Su.S A.H 1 Samavata - - - + + + 2 Shothahara + + + + + + 3 Medya
  • 11. 4 Angamarda prashamana + + + + + + 5 Deepana + + + + + + 6 Bhedana + + - + + + 7 Krimighna + + + + + + 8 Saraka + + + + + + 9 Kushta + + + + + + 10 Vedanasthapana + + + + + + ERANDA TAILA Castor oil is used for medicinal purpose to produce purgation to relieve pains and reduces swelling etc .It is an efficient vatahara drug and so useful in many diseases. Properties : Rasa : Katu ,Madhura Anurasa : Kashaya Guna : Guru ,Snigdha , Sookshma , teekshna ,ushna ,picchila . Doshghnata : Vatanashaka , Kaphavardhaka Rogaghnata : Vatarakta ,Hridroga , Jeernajwara ,krimi ,Vridhiroga , Kushta Oil of red variety of castor seeds is still more penetrating , hot in potency and sticky and has a bad smell .
  • 12. Eranda taila shreshtata : Among all the tailas Eranda taila is sreshta for virechana . Dose : 4-16ml Anupana : Yoosha or Ushna jala Clinical and experimental studies : A study “ Castor oil an update on mechanism of action ’’ castor oil expressed from the seeds of ricinus communis is an effective laxative .The mechanism by which castor oil produces its effect on gutt could involve inhibition of Na++ -ATPase , activation of adenylate cyclase , stimulation of prostaglandins and nitric oxide bio-synthesis .Castor oil changes the intestinal permeability and causes historical abnormalities , but these alteration are not essential for the laxative effect .Platelate activating factor (PAF) is most likely one of the mediation of the castor oil induced damage ,while nitric oxide has a protective role possibly by reducing PAF bio-synthesis . Modern view : Castor oil Biological source : Castor oil is the fixed oil obtained by the cold expression of the seeds of ricinus communis. Geographical sources : Castor seeds are produced in almost all tropical and subtropical countries .In India ,Castor is one of the major oil seed crops ,and India is the second largest producer of castor seeds in the world , producing about 2,80,000 tonnes per annum .Brazil
  • 13. ,USSR ,Thailand ,USA and Rumania are the other countries producing the drug on the large scale .In India it is largely grown in the Andhrapradesh ,Gujrat ,and Karnataka . Preparation of castor oil : Castor oil can be prepared by two different methods , the first being the crushing of whole or decorticated seeds in power driven hydraulic presses and the second one known as Ghani ,which consists of manually operated screw press driven by bullocks .For commercial scale of extraction ,the first method is adopted .The oil thus produced is a non-medicinal castor oil. The seeds are greeded and made freeof impurities like metallic pieces of iron & sand .The seeds are decorticated and hulls are removed .If the seeds are not decorticated ,the manorial value of the cake increases .But for medicinal purposes it is desired that the seeds should be corticated ,as it improves the colour of the oil and also helps in controlling the acid value of the oil. Decorticated seeds are pressed under hydraulic press with a pressure of 2 tonnes per square inch which helps in extracting out 30% of the oil present in the seeds at room temperature .The oil is known as cold drawn oil .Rest of the oil from the seeds is removed by further increasing the pressure ,and sometimes by hot pressing or even by solvent extraction process.The oil thus processed is not suitable for medicinal purposes .The cold drawn oil is then steamed at 800 C to destroy the enzyme lypase and ricin .It is then bleached and de-acidified with sodium bicarbonate to remove the mucilaginous matter present in the oil.Finally it is treated with activated earth or animal charcoal to remove the impurities adsorption and filled into the containers.
  • 14. Organoleptic characters Colour – Pale yellow Odour –Nauseating Taste – First it bland but afterwards slightly acrid and usually nauseating .It is viscous and transparent liquid . Identification : 1. It mixes with half its volume of light petroleum ether (400 to 600 C) 2. Add to the oil equal volume of alcohol ; clear liquid is obtained .On cooling at 00 C and on storage for three hours ; the liquid remains clear. Solubility : It is soluble in alcohol (an exception to the category of fixed oils); miscible in chloroform ,solvent ether ,glacial acetic acid and petroleum ether .It is soluble in mineral oil. Chemical constituents Castor oil chiefly contains triglyceride of ricinoleic acid (about 80%) other glyceroids are also present in the drug , where the fatty acids are represented by icoricinoleic ,linoleic ,stearic and isostearic acids.The viscocity of the castor oil is due to the riceleic acid . Ricinoleic acid : CH3(CH2)5CHOHCH2CH =CH(CH2)7CHOOH Standards 1.Weight per ml – 0.945 to 0.965
  • 15. 2. Acid value – not more than 2 3. Acetyl value – not less than 143 4.Iodine value – 82- 90 5. Saponification value – 177 -185 6.Hydroxyl value- 161 – 168 7. Optical rotation - not less than + 3.50 8.Ignition temperature -449 0 C 9.Density – 1.473 to 1.477 10.Solidifying point – 10 to 18 0 C 11.Viscocity -8 to 0 pieces 12.Refractive index – 1.473-1.477 13.Surface tension at 200 C – 39 dynes/cm 14.Specific rotation - +0.961 to 0.963 Uses  Castor oil is used as catheratic  It is also used for lubrication commercially  Several other forms of castor oil such as dehydrated castor oil (DCO) or hydrated castor oil are used industrially several other purposes .
  • 16.  The catheratic property of the castor oil is due to irritant action of the ricinoleic acid.  Castor oil is often given orally or as aromatic castor oil or in the form of capsules. Therapeutic uses :  It is used in abortificient paste and ricinoleic acid is used in contraceptive jellies.  Atropine and cocaine for ophthalmic purposes are suspended in castor oil  It is also used as an emollient in the preparation of lip-stick and as sulphoresinolate in tooth formulation being strong bacteriocide.  Other cosmetic purposes for which the oil is used includes the perfumed hair oil and hair fixers.  Castor cake is used as a source of enzyme lipase. Sl.No Diseases Authentic books Ch.S Su.S A.H Bp.N SNGN Dh.N MpN YR 1 Gulma + + + + + + + + 2 Vatarakta + + - + - + + - 3 Hridroga + + + + + + + - 4 Jeernajwara + - - - - + + - 5 Krimi + + + + + + + + 6 Kushta - + - + - - - + 7 Vishamajwara - + + + - - + + 8 Vriddhiroga - + + + + + - +
  • 17. SARSHAPA Latin name - Brassica campesatris Family - Cruciferae Vernacular name Hindi : Sarson English : Musterd Kannada : Sasive Synonyms - Katu sneha, Tantubh, sarshap Rasa panchaka Rasa : Katu, tikta Guna : Tikshna, Ruksha (leaves ) , Snigdha (Taila, Beej) Virya : Ushna Vipaka : Katu Doshaghnta - Kapha – vata shamak, Pitta vardhak Parts used – Beeja , Taila Chemical composition Mustard oil is extracted at low pressure at low temperature (40-60oc). The main chemical component of mustard oil is allyl iso thiocynate and it has 30% protein, calcium, phytins, phenolies and natural antioxidants. And it contains high amount of unsaturated fatty acids and good ratio of polyunsaturated fatty acids which is good for heart. Oil is a skin and mucous membrane irritant. Fatty acids composition of mustard oil;- Fatty acid Range
  • 18. 1. Palmitic acid 1-3% 2. Stearic acid 0.4 - 3.5 % 3. Arachidic acid 0.5-2.4% 4. Lignoceric acid 0.5-1.1% 5. Oliec acid 12-24% 6. Erucic acid 40-55% 7. Linolenic acid 7-10% Physical properties;- Refractive index (at 20oC) 1.470 – 1.474 Viscosity (at 20oC) - CPZ 74-120 Solidification temperature 8 to 10oc Solubility soluble in benzene , petroleum ether, acetone. Colour - yellow Smell - specific Transparence - Transparent Moisture content - 0.15 – 0.4% Saponification value - 170 –180 Iodine value - 92 –107 Tocopherol content 31.8 mg% Non saponifiable matters 1-3% Pharmacological & therapeutical uses:-
  • 19. It has Lekhana , Kusthaghna , jantughna ,vednasthapak and Sneha properties . And its oil is a skin and mucous membrane irritant.it is good for heart. Glucinolate, the pungent principle in musterd oil, has antibacterial, antifungal, and anti-carcinogenic properties. SARSHAPA TAILA Sarshapa taila is pungent , hot in potency , penetrating deep into the tissues , mitigates kapha , semen , vata , easily digestable ,produces bleeding diseases , rashes on the skin , leprosy and other diseases , haemorrhoids , ulcers and worms . Biological source : In India several varities of mustard are available which differ from each other in their morphological characters and biological origin .Black mustard is used medicinally , while all other are important as a source of fixed oil and as condiments. Following are a few commercially important species of mustard Types of Species : 1.Black mustard – Brassica nigra linn 2.Gray mustard – Brassica juncea linn 3.Indian rape (Toria) – Brassica compestris 4.Rape seed – Brassica compestris 5.White mustard – Brassica alba Black mustard oil :
  • 20. It is fixed oil obtained from well mustard seeds of Brassica nigra or brassica juncea Method of preparation The oil is prepared from expression Organoleptic characters : Colour -Yellowish Odour – Disagreeable Appearance – Slight viscous Opalesence – Transparent Clarity – Clear Properties of Sarshapa Rasa : Katu Guna : Ushna , Laghu , Snigdha ,Teekshna Virya : Ushna Vipaka : Katu Doshghna : Kaphanashaka , Vatanashaka Chemical constituents : Mustard oil contains glyseroids of arachidic (0.5%) Behenic (2-3%) , Eicosenoic acid (7-8%) , Erusic acid (40-60%) , Lignoceric acid (1-2%) , Linoleic acid (14-18%) , Linolenic acid (6.5 – 7%) , Oleic acid (20-22%) , Myristic acid (0.5 – 10 %) .
  • 21. Specific standards : Specific gravity : 0.914 – 0.923 Unsaponifiable matter – 0.9-1% Refractive index – 1.472-1.4733 Solidifying point – 11 to 170 C Iodine value – 96-124 Saponification value – 173- 184 Uses of Mustard oil : Fixed oil is used as edible oil after refining It is also used as condiment and im manufacture of soap . Refined mustard oil is used in vegetable ghee. Medicinal properties are due to allyl isothiocynate which is local irritant and emetic ,if applied externally. Therapeutic uses Sl.No Diseases Authentic books Ch.S Su.S SNGN Bp.N HS A.H YR Md.N 1 Kusta + + + + + - + + 2 Krimi - + - + + - + +
  • 22. 3 Arsha - - - + - + - - 4 Grahi - - - - + - - + 5 Medhanashaka - - + - + + + - Modern Concept of Oils and Fats Oils and fats are products from vegetable, animal, marine and mineral sources. Oils are liquid at 20°C and fats are in solid state at normal temperature. Natural fats are glycerides of saturated fatty acid or long chain fatty acid for which it is solid and oils are glycerides of unsaturated fatty acid or short chain glyceride for which it is liquid. The two terms are purely conventional since the same substance may be a fat in one climate and oil in another. Thus ghee is a fat in winter and oil in summer. Chemically fats contain more saturated ( i.e. palmitic and stearic ) fatty acids therefore it is hard and melts at higher temperature and oils contain large proportion of unsaturated fatty acid (i.e. oleic) hence it is liquid and melts at lower temperature. The short and medium chain fatty acids are liquids while long chain fatty acids are solids. The high melting point is due to the close packing of the straight chain fatty acid molecules. The solubility in water decreases while melting point and boiling point increases with increase in chain length. Comparison of fats and oils are given in the Table - 23 Table – 23 , Comparison of fats and oils Fat Oil 1.Solid 1.Liquid 2. Contains more saturated fatty acids( i.e. palmitic and stearic ) 2. Contains more unsaturated fatty acids ( i.e. Oleic acid ) 3. Solid due to more saturated fatty acids 3. Liquid due to more unsaturated
  • 23. fatty acids 4. Melts at higher temperature due to more saturated fatty acids 4. Melts at lower temperature due to more un saturated fatty acids 5. Found in animals and plants 5. Found in plants eg. Mustard oil, sesame oil, castor oil, ground nut oil etc. Comparison of unsaturated and saturated fat are given in Table - 24 Unsaturated Fat Saturated Fat 1. It is the fat that the acid radical of which is capable of entering into direct combination with hydrogen and with certain other substances to make saturated compounds. 1. Cannot react in direct combination with other substances. 2. One or more pairs of carbon atoms in the fatty acid radical or radicals are combined with double bonds. At these points addition of hydrogen or other atoms may make a saturated compound. 2. All the carbon atoms in the fatty acid radicals are combined with each other by single bonds. 3. These are liquid. 3. These are solid. 4. More active chemically which has physiology significance. 4. Lesser active.
  • 24. Table .No.25 Classification of Oils and Fats Oil Animal Vegetable Marine e.g. Shark liver oil Cod liver oil Margarine Terrestrial e.g. Sheep foot oil Horse foot oil Egg yolk lard oil Drying oils e.g. Linseed oil Poppyseed oil Semi drying e.g. Sesame oil Mustard oil, Croton oil, Corn oil, Soyabeen oil Non drying e.g. Castor oil Almond oil Arachis oil peanut oil Olive oil Iodine value of Drying oil - 130 - 200 Iodine value of Semi drying oil - 95-130 Iodine value of Non drying oil Less than 95 Fats Animals Vegetable Ghee Butter hard Coconut oil, palm oil Coco Butter Physical properties of oils and fats 1. Fats and oils are solids or liquids having no colour or taste in pure state. 2. They are lighter and insoluble in water and therefore form the upper layer when mixed with it. 3. They are freely soluble in organic solvents like their acetone, alcohol, benzene, chloroform etc called fat solvents.
  • 25. 4. They readily form emulsions when mixed with water in the presence of soap, gelatin or other emulsifier. FUNCTIONS OF LIPIDS The lipids serve the following important functions : 1. Storage form of energy (Triglycerides) 2. Structural components of bio-membranes (phospholipids and cholesterol). 3. Some deposits of lipids may exert an insulating effect in the body, lipids around internal organs like kidney etc. may provide padding and protect the organs. 4. Lipids supply Essential fatty acid (EFA), which cannot be synthesized in the body and are essential in the diet for normal health and growth. 5. Give shape and contour to the body. 6. Metabolic regulators (steroid, hormones and prostaglandin). 7. Acts as surfactants, detergents and emulsifying agents (amphipathic lipids). 8. Act as electric insulators in neurons. 9. Helps in absorption of fat soluble vitamins (A, D, E and K). 10. Adds taste and palatability to food. Table – 26 , COMPOSITION OF OILS AND FATS Name of fatty Acid Saturated fatty acids (%) MUFA (%) PUFA (%) Coconut oil 86x 12 02 Groundnut oil 18 46 36 Gingelly oil 13 50 37 Palm oil 42 52 06
  • 26. Corn oil 13 25 62 Cotton Seed oil 26 19 55 Sesame oil 12 48 40 Mustard oil 34xx 48 18 Safflower oil 09 12 79 Sunflower oil 12 24 64 Butter 75 20 05 Ox (Tallow) 53 42 05 Pig (Lard) 42 46 12 Fish oil 30 13 57 X Saturated fatty acids are medium chain fatty acids. Xx Contains erucic acid, 22c, 1 double bond DIGESTION OF LIPIDS : Dietary lipids are emulsified by the peristaltic movements. The lingual lipase (optimum pH 2.5 - 6) from the mouth enters stomach and acts on short chain triglycerides (SCT) which are present in milk, butter, ghee, coconut oil. Gastric lipase (optimum pH about 5.4) which is acid stable is secreted by gastrin upto 30% digestion of triglycerides occurs in stomach. The pancreatic lipase, cholesterol esterase and phospholipase A2, Bile salts are important in the digestion of lipids. The bile salts present in the bile (sodium glucocholate and sodium taurocholate) have lower surface tension and thus helps in emulsification of fat droplets in the intestine. ABSORPTION OF LIPIDS :
  • 27. Glycerol as well as small chain and medium chain fatty acids (chain length less than 14 carbons) are directly absorbed from the intestinal lumen, into the portal vein and taken to the liver, and are immediately utilized for energy. Long chain fatty acids (chain length more than 14 carbons) are absorbed by forming micelle with the help of bile salts). The theory proposed by Bergstron which won Nobel prize in 1982. Lipids are amphipathic in nature as it contains a hydrophobic tail and hydrophilic head. Amphipathic lipids gets oriented at oil water interfaces with the polar groups in the water phase and the non polar groups in the oil phase. When a critical concentration of these amphipathic lipids are present in an aqueous medium, they form Micelles. Micelle formation, facilitated by bile salts, is the prerequisite for fat digestion and absorption from the intestine. The driving force for micelle formation is hydrophobic since the tail groups cannot break the hydrogen bonds between water molecules and as a result cluster together in close proximity. The products of digestion, namely 2-monoglycerides, long chain fatty acids, cholesterol, phospholipids and lysophospholipids are incorporated into molecular aggregates to form mixed micelle. The micellization helps in dispersing the fatty acid molecules in the aqueous medium of intestinal lumen. In this micellar form, the products of digestion of dietary lipids are presented for absorption at the microvillous surface of jejunal mucosa. Inside the intestinal mucosal cell, the long chain fatty acid (LCFA) are re esterified to form triglyceride. Short chain fatty acids (SCFA) seen in ghee butter etc and middle chain fatty acids (MCFA) seen in coconut oil do not need re-esterification and directly enter into blood vessels SCFA and MCFA are better absorbed than LCFA.
  • 28. Table – 27 , Differences in metabolisms of SCFA and LCFA containing Triglycerides. SCFA and MCFA LCFA 1 Examples Butyric acid (c=4) in butter and lauric acid (c=12) in coconut oil Palmitic acid (C=16) and stearic acid (C=18) in vegetable oils and animal fats. 2 Digestion in stomach Hydrolysed Not hydrolysed 3 Pancreatic lipase Not necessary Essential 4 Bile salts Not necessary Absolute essential 5 Inside intestinal cells TAG is hydrolysed to form fatty acids Free fatty acids are re esterified to form TAG 6 Absorbed to Directly to blood To lymphatics, then to thoracic duct 7 Absorbed as FFA carried by albumin TAG, carried by chylomicrons 8 Immediate fate Oxidised by peripheral cells Deposited in the adipose tissue 9 Carnitine Is not required for oxidation Is required for Oxidation 10 Clinical application No effect on artherosclerosis Leads to hypercholesterolemia
  • 29. and arteriosclerosis Lipotropic agents : Lipotropic factors are agents which are required for the normal mobilization of fat from liver thus preventing accumulation of fat in liver cells. This phenomenon itself is called lipotropism. Choline, Lecithin, Methionine, Betaine, Inositol etc are lipotropic agents. Casein is also a lipotropic agent, probably due to high content of methionine. Lecithin (phosphatidylcholine is abundant in seeds and sprouts) Lecithin has the capacity to lower the surface tension of water and acid in the emulsification and helps in the formation of lipid water mixture. DEGRADATION OF OILS AND FATS / RANCIDITY : Oils and fats tend to spoil on storage due to the production of free fatty acid and by lipase activity or other hydrolytic activity. On storage those changes produce unpleasant taste and odour which is termed as Rancidity of oils and fats. Five factors contribute to the oxidative deterioration of fats and oils. (1) Oxygen or air (2) Heat (3) Light (4) Pro-oxidant metals (5) Time ROUTES TO RANCIDITY :
  • 30. Major routes to oil / fats rancidity are : (1) Hydrolysis (2) Oxidation (3) High temperature polymerization (1) Hydrolysis : Hydrolytic rancidity is due to partial hydrolysis of triacyl glycerol molecular due to traces of hydrolytic enzymes present in naturally occurring fats and oils. Triacyl glycerol Diacyl glycerol Monoacylglycerol Water Fatty acid Water Fatty acid . Fatty acid + Glycerol Hydrolysis is a major problem with short chained fatty acid triglycerides such as lauric acids. Fat degradation reaction of fats and oils with water occurs in triglyceride fraction and is manifested by the formation of free fatty acid. The principles involved in presenting the hydrolytic reaction of fats and oils are (1) Avoidance of water by all possible means.
  • 31. (2) Knowledge and understanding of water can be introduced into a particular system. It should be understood that all fats and oils exhibit a degree of solubility in water, and as a rule of thumb can contain about 0.1% moisture at 20°C. Solubility of water in oil will increase with temperature and decrease as the average chain length of the components fatty acids increase. Sometimes hydrolysis of water with non triglyceride portion occurs which are troublesome or produce undesirable sludge / precipitate and which in extreme cases tends to microbial fermentations which in turn results in enzymatic hydrolysis. This is not a major concern to oils and fats unless the presence of free fatty acid and moisture could lead to increase solubilization of metallic components of the equipment. (2) OXIDATION : Oxidation rancidity is the result of partial oxidation of unsaturated fatty acid with resultant formation of epoxides and peroxides of small molecular weight fatty acid by peroxides and free radical. Oxidation causes off flavor instability and primary focus of most analysis. The degree of oxidation of fats and oil is determined by analyzing the artifacts formed. These may be divided into two classes viz primary and secondary. Primary oxidation products are those which are formed initially from the reaction of oxygen, free radicals and fats. These are unstable and decompose to form secondary reaction product. Oxidation occurring in processed oils are mainly due to - 1. Auto-xidation 2. Photo-oxidation 3. Enzymatic oxidation 1. Auto-oxidation :
  • 32. Auto-oxidation are the process through which free radicals are formed by the loss of hydrogen atom from methylene group adjacent to a double bond. This is supposed to be initiated by light heat etc. Through this free radical chain reaction involving initiation, propagation and termination occurs. R'CH2CH = ChCH2R" R' CH CH = CH CH2 R" heat, metals, O2 Atmosphere oxidation converts this free radicals into peroxide which is also a free radical. R' CH2 CH = CH CH2R" + O2 R' CH CH = CH CH2 R" 00 - X The peroxide radical again reacts with another molecule of the original oxidisable substance to produce a hydro-peroxide, another free radical. R'CH CH = CH CH2 R" + R' CH CH = CH CH2 R" 00-X 00H R' CH CH = CH CH2 " + R' CHC = CH CH2 R" Such a long chain reaction provides and ultimately the hydro-peroxide decomposed to produce the undesirable aldehydes and esters. The overall preponderance of oxidation reaction of fats and oils is related to fatty acid composition and more specifically to the type and amount of unsaturation. Thus oils and fats with higher degree of unsaturation or higher iodine value will peak up oxidative rancidity earlier. Initially oxidation of fats is usually slow, but once the peroxide formation reaches a certain level the rates of oxidation increases and fat soon begins to give rancid taste and odour.
  • 33. 2. Photo-xidation Photoxidation is much faster reaction that catalyzes the attack at the double bond by singlet oxygen formation and may initiate the slower auto-oxidative reaction by formation of trace amounts of hydro-peroxides made possible by pigments (chlorophyll) in the finished oil. 3. Enzymatic oxidation The most important classes of enzymes causing lipid oxidation are lipoxygenase. These enzymes are quite common in the plant world and thus are present in all of the vegetable oil seeds . Lipoxygenase only acts on the polyunsaturated fatty acids and catalyzes the addition of oxygen to the alpha-methylene carbon, creating hydro=peroxides, similar to those found during autoxidation. These enzymes do not survive processing because of their destruction by heat. Hence inorder to avoid enzymatic oxygen the oil should be heated to temperature for the complete removal of moisture . Tests of Rancidity : Following are the tests to check the rancidity in oil and fat. 1. Measurement of acid value / free fatty acid 2. Peroxide value 3. Colorimetric method 4. Kreis method 5. Para anisidin test 6. Thiobarbituric acid number. STABILISATION OF OILS / FATS : Methods available to protect fats and oils against oxidative deterioration during the unit processing operations are as follows :
  • 34. 1. Use of adequate temperature processing and storage. 2. Use of inert gas blanketing during storage. 3. Avoidance of light. 4. Avoidance of prooxidants e.g. metals like copper, lead. Antioxidants can be used as preventive measure against rancidity and have shelf life can be enhanced.
  • 35. Bibliography 1. Agnivesha. Charaka Samhita. Redacted by Charaka and Dridhabala with Ayurveda Deepika Commentary by Chakrapanidatta and Vidyotini Hindi Commentary by Pt.Kashinath Shasthri.Varanasi: Chaukambha bharati academy; 2009.reprint 2. Vagbhatacharya, Ashtangahridayam with commentaries of Sarvangasundara of Arunadatta and Ayurveda Rasayana of Hemadri, Annoted by Dr.Annamoreshwar kumte and Krishna ramachandra shastrinoure edited by Pt.Harisadashiva shastry Paaradakarabhishagaacharya, Varanasi, Choukhambasuarabharati prakashana, reprint 2010. 3. Vriddha Vaghbhatacharya , Ashtanga Sangraha , Induvirachita ‘ Shashilekha’ commentary edited by Dr. Shivaparsad sharma , 1st edition ,Varanasi ; Chaukhambha Sanskrit series office. 4. Sushruta , Susharuta samhita ShriDalhanacharya virachita and Nyayachandrikapanjika of shriGayadasacharya on nidanasthana, with the Nibandhasangraha commentary edited by vaidya Yadavjitrikamjiacharya,Varanasi, choukhambasurabharati prakashan, reprint 2012. 5. Bhavaprakasha Bhavamishra ,Bhavaprakash edited with The vidyotini hindi commentary By Sri Brahamasankara Mishra , and Rupalalji vaisya ,8th edition ,Varanasi; Chaukhambha Sanskrit sansthan ,1998, Purvardha 6. Sri Chakrapanidatta. Chakradatta with Vaidyaprakasha Hindi commentary. by Dr.Indradev Tripathi.edited by Prof.Ramanath Dwivedy. Varanasi: Chaukhamba Sanskrit Bhawan; Reprint- 2010
  • 36. 7. Kaviraj Shri Govindadassen, Bhaishajya Ratnavali. edited with Siddiprada Hindi commentary, by Prof. Siddhinandan Mishra, Varanasi, Published by Chaukhamba surbharti prakashan, reprint 2015,chapter 5 8. Ananymous. Yogarathnakar vidyotini hindi tika sahit, edited by Bhisaga Ratna Bhramha Shankar Sastri. 6th edition,Varanasi: Choukambha prakashana ,Reprint 2015 9. P.C.sharma,M.B.Yelne,T.J.Dennis.Database on medicinal plants used in Ayurveda & siddha.CCRAS:New Delhi;Reprint 2005. 10. D.M. Vasudevan, S. Sreekumari- ' Text Book of Biochemistry for medical students 3rd edition, New Delhi ;Jaypee Brothers, Medical Publishers (P) Ltd