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1) 4th Semester V.O. Lect. 1
1) 4th Semester V.O. Lect. 1
1) 4th Semester V.O. Lect. 1
Introduction:
• Volatile oils are the odorous principles found in various plant parts.
• They are called volatile oils or ethereal oils as they evaporate when
exposed to air at ordinary temperatures.
• They are also known as essential oils as they represent the “essences”
or the odorous constituents of plants.
• They are aromatic complex mixtures of different groups of organic
compounds called terpenes.
• Terpenes consist of either carbon and hydrogen only
(hydrocarbons) or carbon, hydrogen, and oxygen
(oxygenated compounds) such as alcohols, phenols, esters,
ketones, aldehydes, etc.
• The odour and taste of volatile oils are mainly attributed to their
oxygenated compounds, e.g. Cinnamon oil (cinnamic
aldehyde), Clove oil (eugenol), etc.
Volatile oils differ from fixed oils in the following:
1. Volatile oils are fragrant, while fixed oils are not.
2. Fixed oils are nutritive (high calories), while volatile oils are non-nutritive.
3. Volatile oils can be distilled, while fixed oils cannot.
4. Fixed oils consist of glyceryl esters of fatty acids, while volatile oils consist of
terpenes.
5. Fixed oils can leave permanent grease spots on a filter paper, while volatile oils
cannot.
6. Fixed oils can be saponified with alkalies, while volatile oils cannot.
7. On exposure to light and air, fixed oils become rancid, while volatile oils undergo
oxidation and resinification.
Distribution and localization of volatile oils:
• Volatile oils occur mainly in higher plants; there are about 17500 aromatic
species.
• Myrtaceae, Lauraceae, Rutaceae, Lamiaceae, Asteraceae, Apiaceae,
Poaceae, Zingiberaceae, and Piperaceae are common volatile oils-
producing families.
Volatile oils accumulate in all types of vegetable organs, such
as:
- Flowers (Chamomile, Rose, Jasmine)
- Leaves (Citronella, Eucalyptus)
- Barks (Cinnamon)
- Woods (Rosewood, Sandalwood)
- Roots (Vetiver)
- Rhizomes (Ginger)
- Fruits (Anise, Star anise, Fennel)
- Seeds (Nutmeg, Cardamom)
Volatile oils are localized in different secretory structured, such
as:
◦ Oil cell (e.g. Lauraceae or Zingiberaceae)
◦ Glandular trichomes (e.g. Lamiaceae)
◦ Secretory cavities (e.g. Myrtaceae or Rutaceae)
◦ Secretory canals (e.g. Apiaceae or Asteraceae)
Functions of volatile oils in plants:
• Allelopathic, particularly as germination inhibitors.
• Protection against insect, fungi, bacteria, and sometimes animals.
• Attraction of different pollinating insects.
◦
General uses of volatile oils:
1. In manufacturing of perfumes, cosmetics, and cleaning products.
2. In preparation of disinfectant agents with antiseptic properties.
3. As antimicrobials for food preservation.
4. Flavoring agents for foods, candies, gum, confectionary, toothpastes, and
various pharmaceutical products.
5. As insect repellent and green pesticides.
6. Antibacterial, antifungal, and antiviral agents.
7. Carminative, antispasmodic, and bronchodilator (smooth muscle relaxant).
8. In aromatherapy and massage therapy (forms of complementary medicine).
Physical properties of volatile oils:
1. Almost with fragrant odours.
2. Easily volatilized at room temperature.
3. Liquids at room temperature except Anise oil (solid until 15 °C and melts at 16 °C)
and Rose oil (solid until 18 °C and melts at 19 °C).
4. Colorless liquids but some oils are colored, e.g. Chamomile oil (blue in color).
5. Their density is lower than water, with the exception of Clove and Cinnamon oils
are heavier than water.
6. They show high refractive indices and optically active.
7. Soluble in most organic solvents.
8. Sparingly soluble in water; however, they are soluble enough to impart a distinct
fragrance to water.
Stability of volatile oils during storage:
➢The exposure of volatile oils to heat, light, and air during storage will negatively
affect their chemical composition.
➢These chemical changes of volatile oils will result in deterioration of their taste
and fragrance (due to oxidation), viscosity (due to polymerization or
resinification), and therapeutic use (due to skin sensitization and dermatitis).
Stability of volatile oils during storage:
➢Some components of volatile oils can be converted
into toxic derivatives or isomers under these
conditions.
➢Accordingly, volatile oils should be stored in well-
closed amber glass, cobalt blue or aluminum
bottles. Bottles should also be filled to the neck to
expel all oxygen and stored at low temperatures
(e.g. refrigerators).
1- Distillation methods:
a) Water distillation
(hydrodistillation):
1-The dried plant material is immersed in
water saturated with NaCl.
2- Water distillation is suitable only for thermally stable V.O. Under the drastic
conditions of distillation, unstable V.O. will undergo degradation.
3- This method is used for dried plant material, which keep their odour for
long time (oils are secreted from internal secretory structures). Thus,
preparation of the volatile oil is under drastic conditions (boiling).
3- Steam is forced through the plant material and the oil is obtained as
before.
2- Water is heated and at the same time, the steam generated elsewhere is
piped into the container containing the macerated material.
4- This method provides some sort of heat control to prevent overheating and
decomposition of V.O.
◦ Using very high temperatures will not only affect the oil constituents (hydrolysis
or decomposition) but may also affect the other plant components.
◦ Oil recovery: the collected distilled water and V.O are received in the oil
separator, where the oil can be easily separated. However, the water will keep
some of the obtained volatile oils either in solution or suspension, leading to
loss of some volatile oils; therefore, Cohobation is recommended, where the
water can be freed from the oil by saturation with NaCl or by extraction with an
organic solvent.
2- Expression methods:
- Before the discovery of distillation, all essential oils were extracted by pressing.
- These methods are used for preparation of V.O occurring in the rind of fruits,
e.g. peels of orange, lemon, bergamot, etc. They are also the most suitable
method for sensitive oils, such as that in the rind of Citrus fruits. They include:
a) Sponge method:
◦ 1- It is used on small scales and mainly for citrus fruits.
◦ 2- The rind is squeezed in front of a sponge and then transferred to a vessel in which it
is left for separation.
b) Scarification method:
◦ The plant material, e.g. entire fruits, is transferred to a funnel of tinned copper in which
the upper surface bears numerous strong pins to penetrate the outer layers of the
fruits. The oil is collected and left to separate from the juice or the moisture.
◦ c) Rasping process:
◦ 1- A very old technique in which the peel containing the oil glands is removed
by rasping with graters.
◦ 2- The raspings are strongly pressed in bags of horse-hair and the oil is then
collected.
◦ d) Machines:
◦ The most widely used expression method nowadays. Large amounts of plant
materials are pressed by machines and the oil is obtained after centrifugation.
3- Extraction methods:
◦ Volatile oils which decompose by heat or present in trace
amounts in their plant materials are usually prepared by this
process. Extraction methods include:
b-2) Digestion:
This process is similar to maceration but moderate heat is applied to aid
extraction.
b-3) Enfleurage:
◦ - This process was once used for extraction of volatile oils
of delicate flowers, e.g. Jasmine.
◦ - Two thin layers of inodorous fat (beef tallow or lard) are
spread and flowers are then spread lightly between them.
◦ - After complete extraction, the flowers are removed
(defleurage) and replaced with new flowers.
◦ - With prolonged contact, the fat layers become saturated
with the volatile oil of the flowers.
◦ - These fatty layers, called pomade, are extracted with
alcohol (stirred with alcohol that dissolves the oil leaving
the fat).
◦ - The oil is separated by fractional distillation from alcohol.
The resulting oil, which is free from both fat and alcohol, is
called absolute or enfleurage.
b-4) Pneumatic method:
◦ The same principle of enfleurage method but includes passing a current of
warm air through the flowers. The air loaded with the oil is passed through a
spray of melted fat in which the oil is adsorbed and separated as before.
c) Extraction with a supercritical fluid (supercritical gas
extraction):
◦ At the supercritical pressure & temperature, gases have two important
characters: flow ability like a gas & extraction ability like a solvent. Thus,
supercritical gases/fluids can defuse through plant tissues and extract essential
oils.
◦ Carbon dioxide (CO2) is the most used supercritical fluid. Extraction conditions
for supercritical CO2 are above the critical temperature of 31 °C and critical
pressure of 74 bar.
4- Enzymatic hydrolysis:
Terpenes:
◦ Volatile oils contain complex mixtures of several groups of organic compounds
called terpenes.
◦ Terpenes are natural products that are biosynthetically derived from isoprene.
Terpenoid compounds consist of a number of isoprene units.
◦ The isoprene unit is a branched-chain, five-carbon unit containing two
unsaturated bonds (2-methyl-1,3-butadiene).
◦ According to the total number of carbon atoms, terpenes are
classified into:
◦ Terpenes found in volatile oils are often monoterpenes and sesquiterpens.
They occur as acyclic or cyclic (monocyclic, bicyclic or tricyclic) hydrocarbons
and as oxygenated derivatives, such as alcohols, aldehydes, ketones,
phenols, oxides, peroxides, and esters.
◦ Structure determination of terpenes:
A) Analytical methods:
◦ 1- Elemental analysis: a technique used to determine the molecular formula
of the compound.
◦ 2- The degree of unsaturation: determined either by quantitative catalytic
hydrogenation or with organic per acids as follows:
B) Chemical methods:
1- Functional group determination:
◦ a- Alcohols are insoluble in KOH and Na2CO3.
◦ b- Phenols are soluble in KOH and insoluble in Na2CO3.
◦ c- Carboxylic acids are soluble in both KOH and Na2CO3.
2- Unsaturation:
by formation of additive crystalline products with Br2 or HBr.
3- Ozonolysis:
a valuable method for cleavage of ethylenic bonds.
C) Spectral techniques:
1- UV analysis: for aromatic and polyunsaturated compounds.
2- IR: for determination of functional groups.
3- NMR: for full structural assignment by 1H and 13C NMR methods…etc.
4- Mass spectrometry (MS):
◦ a- High Resolution MS (HRMS) for determination of the molecular formula.
◦ b- Electron Impact MS: for confirmation of the structural identity from the fragmentation pattern
of each component.
5- GC/MS: a combination of gas chromatography and MS spectral analysis for structure
assignment (preliminary investigation).
6- X-ray crystallography: to give the final structure with its absolute configuration (the most
precise method).
◦ Determination of the percentage of
various volatile oil constituents:
◦ The composition of V.O. is usually investigated
by GC and GC/MS analyses.
◦ The percentage of each component in the V.O.
can be calculated from the obtained GC
chromatogram according to the following
equation:
◦ AUP of the compound x 100/ Total AUP of
all oil components
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