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Anna Drew
with grateful acknowledgement for inspirational teaching received at The School of Pharmacy, University of London
LIPIDS
Simple: fixed oils, fats, waxes Complex: phosphatides, lecithins
may contain P, N as well as C, H, O
3 fatty acids may be involved => triglyceride (main component of oils and fats) some may exist as free acids [Fish oils may have 12 fatty acids which vary]
Mixed triglyceride
fatty acid groups different more usual in nature
Saturated or unsaturated:
unsaturated acids: oleic, linoleic, linolenic, palmitolinic saturated acids: palmitic, myristic, stearic
most vegetable products contain a high number of triglycerides with unsaturated fatty acids liquid most animal products opposite where large number of unsaturated fatty acids readily oxidizes eg whale, fish oils, linseed
Determination of structure
by hydrolysis or saponification in 2 ways:
i) Alkaline hydrolysis with KOH
splits triacylglycerol into parent glycerol and releases all fatty acids arrangement of fatty acids is unknown
Chemical tests
solubility freezing point, melting point refractive index (and sometimes optical rotation) density
Waxes
contain appreciable quantities of
esters derived from higher monohydric alcohols (one OH group) of the methyl (1y) alcohol series combined with fatty acids (C16 C32)
Uses
readily absorbed through skin
ointments
food source
eg peanut oil may contain essential fatty acids (linoleic acid, arachidonic acid required in prostaglandin formation)
Olive oil
salad oil, sweet oil From ripe fruits of Oleo europoea (Oleaceae)
Mediterranean, California native of Palestine, known in Egypt in 7th century B.C., introduced into Spain early on
pale yellow with greenish tinge (chlorophyll and carotene) bland, slight odour, goes pasty/cloudy at 10oC
tested for absence of arachis oil, cotton-seed oil, sesame oil, peanut oil and tea-seed oil (Camellia sasanqua) Composition:
Arachis oil
From seeds of Arachis hypogaea (Leguminosae) groundnut cultivated in tropical Africa, India, Brazil, southern USA and Australia worlds 4th largest source of a fixed oil seeds contain 40-50% oil fruits shelled by a machine kernels difficult to express; crushed and cooked at low pressure seed cake fed to cattle
Composition:
oleic acid ~ 60% linoleic acid 24% palmitic acid 9% arachidonic acid
acid and saponification values similar to olive oil if fatty acids are separated (hydrolysis) the presence of arachidonic acid gives a melting point >710C
used as a test for adulteration of olive oil
Castor oil
From seeds of Ricinus communis (Euphorbiaceae) India, Africa, Europe Contains ricinoleic acid 91%, glycerides GU3
must be free of ricin
pale yellow, very viscous, acrid tasting soluble in ethanol (unlike most oils) due to so much hydroxy- acid Used in toothpaste, nail varnish remover, lubricant industry and pharmacy (as derivatives)
Almond oil
From Prunus amygdalus v. amara (bitter used in pharmacy), v. dulcis (sweet) native to Far East, grown in Mediterranean, N.California Oil is highly unsaturated
with oleic acid 77%, linoleic acid 17% 83% GU3, 17% GSU2
Bitter almond oil also contains amygdalin (glycoside) which decomposes to benazldehyde + HCN Used in pharmacy in oily injections and ointments
prone to oxidation so has to be kept air-free or goes rancid transfer to smaller bottle to exclude air
Theobroma oil
Cocoa butter From seeds of Theobroma cacao (Sterculaceaea) Central America, also cultivated in Brazil, W.Africa (Nigeria) Solid oil
high steric and palmitic acid content (35%, 25%), oleic acid 3% GS2U 52% melting point 31-350C low iodine value because saturated most expensive commercial fixed oil (adulterated)
Animal products
Cod and Halibut liver oils
mixed triglycerides, mainly unsaturated C16-22 acids and decahexanoic acid Used for Vitamin A and D content (halibut > cod)
Beeswax
yellow and white from honeycomb simple esters of 1y alcohols with a high degree of myricyl palmitate (80%) (C15H31OOC30H61) ester:acid ratio value 3.3-4.2 Used in paraffin ointment, plasters and enteric coating
Carnuba wax
an adulterate of beeswax From the cuticle of the South American palm Copenicia cerifera Used in tablet coatings
Spermaceti
From the head of sperm (Physeter macrocephalus) and bottle-nosed whales (Hyperodon rostratus) just above right nostril) 500lb from 1 whale simple esters of cetyl alcohol CH3(CH2)4CH2OH cetyl palmitate, cetyl myistate 90-93% no longer used pharmaceutically, can be replaced by jojoba oil
Wool fat
From the wool of sheep (Ovis aries) Complex composition:
esters of cholesteryl and isocholesteryl + estolidic 32-33% esters of normal aliphatic alcohols with fatty acids 48-49%
Extraction
enzymes in cells can break down oils in cells some oils highly unsaturated and easily oxidized heat in air > rapid oxidation [1] Cold expression [2] Steam treatment + expression [3] Solvent extraction
Olives
put into press light pressure applied gives the 1st grade oil used in pharmacy oil washed to remove pigment floats to the top and is skimmed off 30-40% oil recovered not economical
Cocoa seeds
fat is solid so cant cold express use hot expression with steam treatment oil is a byproduct of the cocoa industry
Spermacetin
ensure well separated from normal triglycerides washed with alkali
Wool fat
has to be cleaned up acidified to precipitate waxes free fatty acids removed by forming salts wax extracted with acetate product can be bleached to give light yellow colour or left as dark yellow wax
Volatile oils
different from fixed components of plants that are
highly odiferous generally occur as they are secreted in oil cells in specialised structures
ducts, cavities, glandular hairs
mainly terpenoid
some phenol ethers and phenols
Terpenoids
based on the 5C isoprene unit
Monoterpenes
most important, most volatile
di-, tri-, sesquiterpenes also important
Monoterpene components
Hydrocarbons
Alcohols
Aldehydes
Citral
Ketones
Esters
Oxides
Sesquiterpenes (C15)
Hydrocarbons Phenols Phenolic esters
Anethole
Families
Economically only a few family groups are commercially useful [1] Labiatae
Lavender, Mentha Sp.
large number, tend to hybridise oil occurs in special organs
synthesized in glandular trichomes (mint)
[2] Umbelliferae
Fruits (best if ripe): anise, caraway, fennel, coriander
found in vittae in the outer layer is characteristic steam distill to remove oils
[3] Pinaceae
Pine, juniper
found in resin ducts in outer old xylem or bark released when bark removed
[4] Rutaceae
Citrus fruits
typical ductless sacs in outer part of fruit rind found at various depths before albino layer (white bitter pithy part) oil is there under pressure and will burst open when rasped less stable, need more care
[5] Lauraceae
Cinnamon, camphor
from region immediately below bark
Method of extraction
depends where oils lies and its stability Steam distillation
gentle, herb + water heated and oil distilled over
Water distillation
wood chips in chamber and heated until water distills over crushed sample must be stable
Cold expression
citrus fruit oil (lemon, orange, bergamot) rasping process breaks oil sacs in rind pour cold water over and then separate oil and water
Enfleurage
petals (rose) placed between glass sheets covered in sheep or pig fat oil seeps into fat and can be extracted with methanol
Destructive distillation
produces a different product from the one started with pine and juniper heated to exclude air over
aqueous part - wood naphtha (ethanol and crude acetic acid) to attract juniper oil non-aqueous part resin (pine tar) to attract C5-C20 molecules including monoterpenes like a fractional distillation
Uses
as inhalations, orally, gargles, mouthwashes, trans-dermally
Rutaceae
Citrus oils
D-limonene 90%, citral 4% + esters, pinene, d-limonene (small amount) high proportion of limonene desirable but a lot is removed after isolation by distillation under reduced pressure leaves oil high in citral which deteriorates on storage giving a turpentine odour
Umbelliferae
Pimpinella anisum (anise), Foeniculum vulgare (fennel)
90% anethole some fennel variaties contain fenchone giving a bitter taste
(sesquiterpene)
Clove
Syzygium aromaticum eugenol 82% used on sore teeth to deaden pain
Eucalyptus oil
1,8-cineole 70%
[3] Perfumes
Rose oil
Rosa gallica, R. damescena trans-geraneol and isomer cis-nerol