Terpenoids

DESTA S.

09/08/2023 TERPENES 1
 Terpenes
2

The name ‘terpene’ is derived from the Greek

word ‘terebinth’.

Terebinth is a type of pine tree from which

terpene-containing resins are obtained.

TERPENES 09/08/2023
 What are terpenes?
3

Natural organic compounds.

Components of a variety of fruit and floral flavours and

aromas.

Used in perfumes, essential oils and medicines.

TERPENES 09/08/2023
 Essential oils contain terpenes
4

Lavender – used to relieve tension.

Ylang-ylang – used to treat anxiety.

Lemon oil – aids good circulation.

Essential oils often contain a mixture of terpenes.

TERPENES 09/08/2023
 Spices contain terpenes
5

Terpenes in plants can be oxidized to produce the

compounds responsible for the distinctive aroma
of spices.

Terpenes containing oxygen or other functional

groups are known as ‘terpenoids’.

Common spices containing terpenes include

cloves, cinnamon and ginger.

TERPENES 09/08/2023
 Terpenes are unsaturated
6

Terpenes are unsaturated compounds.

All terpenes are built up from units of

isoprene.

TERPENES 09/08/2023
 Isoprene
7

Isoprene is the common name for

2-methylbuta-1,3-diene

CH3 H3C CH2

H2C C CH CH2 C CH

H2C

TERPENES 09/08/2023
 Isoprene
8

Head Tail

CH3 CH2

C CH =

CH2

Isoprene
(2-methylbuta-1,3-diene)

One isoprene unit contains five carbon atoms

TERPENES 09/08/2023
 Building terpenes from isoprene
9

Isoprene units can be linked:

head to tail to form linear terpenes

in rings to form cyclic terpenes.

TERPENES 09/08/2023
 Myrcene – a linear terpene
10

Head Tail Head Tail

H3C CHH23C CH2 H3CCH2 CH2

C CH C CH C
C CH
CH

H2C H3C HH22CC

• Myrcene is a component of plants, including bay,

ylang-ylang and thyme.
TERPENES 09/08/2023
 Limonene – a cyclic terpene

H3C CH2
C

CH
H2C CH2

H2C CH
C

CH3

Limonene
(skin of citrus fruits)

TERPENES 11 09/08/2023
 Menthol – a cyclic terpenoid
12

H3C CH3
CH This terpene has been
oxidised to a terpenoid
CH OH
H2C CH

H2C CH2
CH

CH3

Menthol
(peppermint)

TERPENES 09/08/2023
 Absinthe – a cyclic terpenoid
H3C CH3
CH This terpene has been
C oxidised to a terpenoid
H2C CH2

HC C
CH O

CH3

Thujone
(Absinthe)

TERPENES 13 09/08/2023
 Camphor – a cyclic terpenoid
CH3
H3C
C

CH
CH2 CH2
C
H2C C
H3C
O

Camphor
(Camphor tree)

TERPENES 14 09/08/2023
 a-Selinene – a cyclic terpene
15

CH3
CH2
3 isoprene units
CH2
H2C C CH2
15 carbon atoms
H2C CH C CH2
C CH2 C
H
CH3 CH2

-Selinene

TERPENES 09/08/2023
 β-carotene – a linear terpene
16

H3C CH2
C CH2
CH3 CH3
H3C CH3
CH C CH2
CH CH CH
C CH C CH C CH CH C
C CH C
H2C C CH CH CH CH CH
H3C CH3
CH3 CH3
H2C C
CH2 CH3 -carotene

8 isoprene units

40 carbon atoms
TERPENES 09/08/2023
 TERPENS
17

 any of a class of hydrocarbons occurring widely in plants and

animals and empirically regarded as built up from isoprene, a
hydrocarbon consisting of five carbon atoms attached to eight
hydrogen atoms (C5H8). The term is often extended to the
terpenoids, which are oxygenated derivatives of these
hydrocarbons.
 Biological formation of the terpenes occurs by the combination
of two molecules of acetic acid to give mevalonic acid (C6H12O4)
and conversion of the latter to isopentenyl pyrophosphate, which
contains the five-carbon isoprene skeleton. Further
transformations of the isopentenyl compound yield the true
terpenes and the terpenoids.
TERPENES 09/08/2023
 18

The true terpenes are usually grouped according to the number of

isoprene (C5H8) units in the molecule: monoterpenes (C10H16)
contain two such units; sesquiterpenes (C15H24), three; diterpenes
(C20H32), four; triterpenes (C30H48), six; and tetraterpenes (C40H64),
eight. Rubber and gutta-percha are polyterpenes in which 1,000–
5,000 isoprene units are joined in a long chain. Monoterpenes,
sesquiterpenes, and diterpenes are abundant in the essential oils
of plants: turpentine contains several monoterpenes, and the rosin
acids are diterpenes. Vitamin A is another important diterpene.
The triterpene squalene, obtainable from shark-liver oil, may be
converted to cholesterol and many other steroids. The carotenoid
pigments are the best known tetraterpenes.
TERPENES 09/08/2023
 ISOPRENOIDS
19

 Isoprenoids are a major class of nonsaponifiable lipids that occur

in plants, animals, and bacteria. They are characterized by chains
consisting of modular groups of five carbon atoms in which the
typical pattern has four of the carbon atoms in a linear chain and
a single carbon attached at the carbon one position removed from
the end of the chain, shown schematically below.

TERPENES 09/08/2023
 20

The term isoprenoid is derived from the name of the five-carbon,

doubly unsaturated branched hydrocarbon isoprene, which could
in principle be the simplest monomeric chemical precursor for
this class of compounds.

TERPENES 09/08/2023
Classification
The isoprenoids are broadly classified according to the number
of isoprene (C5H8) units they contain, and they range in size
from volatile oils of molecular formula C10H16 to giant molecules
such as that of natural rubber, which contains about 4,000
isoprene units. The following classes are recognized:
monoterpenes, C10H16; sesquiterpenes, C15H24; diterpenes,
C20H32; triterpenes, C30H48; tetraterpenes, C40H64; and
polyterpenes, (C5H8)n. Many of the isoprenoids possess carbon
skeletons that may be regarded as built up from isoprene units
linked “head to tail”; that is, carbon atom 1 of one unit is
bonded to carbon atom 4 of the next.

09/08/2023 TERPENES 21
 Formation of additional bonds in a variety of ways leads to
monocyclic, bicyclic, and further subclasses in which one,
two, or larger numbers of rings are present. β-Myrcene, an
acyclic monoterpene; limonene, a monocyclic monoterpene;
α-pinene, a bicyclic monoterpene; and vitamin A, an
oxygenated monocyclic diterpene, exemplify this further
classification; the dotted lines in the structural formulas
indicate the division of the carbon skeletons into isoprene
units.

09/08/2023 TERPENES 22
 monoterpenes

09/08/2023 TERPENES 23
 sesquiterpenes triterpene

diterpene

tetraterpenes

09/08/2023 TERPENES 24
 Polyterpenes
Rubber, which occurs in the latex of the rubber tree, is
a polyterpene hydrocarbon, (C5H8)n, in which n is
4,000–5,000. Chemical degradation by oxidation and
X-ray-diffraction studies have revealed a repeating
unit in rubber. Division into isoprene units is
indicated.

09/08/2023 TERPENES 25
 Questions
 Which unit makes up every terpene?

 How many carbons are there in an

isoprene unit?

 What is the systematic name for

isoprene?

 What is an oxidised terpene known as?

26 TERPENES 09/08/2023
Answers
 Which unit makes up every terpene?
Isoprene unit
 How many carbons there are in an isoprene unit?
Five
 What is the systematic name for isoprene?
2-methylbuta-1,3-diene
 What is an oxidised terpene known as?
Terpenoid

27 TERPENES 09/08/2023
 Carotenoids

09/08/2023 TERPENES 28
 What are carotenoids?
• Tetraterpenes (C40)
• Long symmetrical chains of conjugated hydrocarbons
usually with cyclization on either end.
• Rings often have alcohol, epoxide, or carbonyl
groups
• Highly conjugated systems result in brightly colored
yellow and orange compounds.

09/08/2023 TERPENES 29
 Carotenoids
Tetraterpenes
Plant products
Biological functions

Photosynthesis
Provitamin A
Vision
Cell-cell communication
Cell membrane
Cancer prevention
Antioxidants ( CVD’s)

Atherosclerosis: CVD: Dietary antioxidants: Antioxidant vitamins

09/08/2023 TERPENES 30
Lycopene and b-carotene are tetraterpenes called
carotenoids

09/08/2023 TERPENES 31
 Biosynthesis:

• Tail-to-tail coupling of 2 molecules of C20

geranylgeranyl diphosphate (GGPP)
• Result:

---In plants and fungi (cis) Z-phytoene.

---In bacteria: (trans) E-phytoene.
• Dehydrogenation leads to lycopene.

09/08/2023 TERPENES 32
 Biosynthesis:
• The E (trans) form of Phytoene is
produced by bacteria
• The Z (cis) form of Phytoene is
produced in plants and fungi.
• Isomerization to E (trans) occurs
during desaturation process, leading
to straight chain carotenoid
lycopene, found in tomato
(Lycopersicon esculente)
• Conjugation is extended by a
sequence of desaturations removing
pairs of H’s alternately from each
side of triene system.
• Central conjugated triene prevents
the type of folding and multiple
cyclizations seen with squalene
09/08/2023 TERPENES 33
 Cyclizations lead to the variety of carotenoid
structures

Carrots
(Daucus carota)

Oxygenated carotenoids
= xanthophylls
(more common in fruits)
maize
mango, persimmon
spinach

brown
algae Capsicum
09/08/2023 TERPENES
(peppers)
34
 on
m m
rsi
pe

09/08/2023 TERPENES 35
 Some common carotenoids with cyclic end
structures:

09/08/2023 TERPENES 36
 Health Benefits:
• Carotenoids possess high antioxidant capacity, with
ability to absorb harmful UV light
• Observed beneficial bioactivities may or may not be
linked to the antioxidant properties
• Higher total carotenoid (b-carotene, a-carotene, and
lycopene intakes associated with lower abdominal fat
mass
• Higher lycopene intake related to lower serum
triglyceride concentrations – Sluijs et al; Journal of Nutrition
May 2009, 139 (5), 987-992.

09/08/2023 TERPENES 37
 Health Benefits:
• High blood serum levels of Lutein correlate with
a reduced risk for age-related macular
degeneration (Breithaupt, et al; J. Agric. Food Chem. 2002; 50,
7175-7181 )
• Increased intake of carotenoids, particularly
lycopene, associated with protection against loss
of bone density at the lumbar spine in women and
the hip in men (Sahni, et al; American Journal of Clinical
Nutrition; Jan 2009; 89(1), 416-424)
• Carotenoids can modify membrane structure and
properties, affect human immune response, cell-
cell signaling (Hurst, ed, “Methods of Analysis for Functional
Foods and Nutraceuticals”, 2nd TERPENES
09/08/2023 edition, CRC Press, 2008.) 38
Age related macular degeneration (AMD) is the leading cause
of vision loss .
It is a progressive eye disease that leads to significant visual
impairment of one's central vision, which can make it difficult to
recognize faces, read, or drive.

09/08/2023 TERPENES 39
 Good for your eyes and your colon?
• Lutein and zeaxanthin are present in the
human eye (macula) and are thought to
protect the retina from oxidative stress
• Dietary intake is correlated with a lower
incidence of macular degeneration, a
common eye ailment in aging population
• A 2008 Korean study found these carotenoids
also block growth of colon cancer cells (Cha, et al,
J. Agric. Food Chem)
• Lutein and zeaxanthin extracted from algae Cranberries
induced apoptosis in colon tumor cells contain
lutein too!
OH

HO 09/08/2023 TERPENES 40
 Roles of carotenoids in nature:
• Antioxidants, protection from radiation
• Cleavage of b-carotene by b-carotene-15,15’-dioxygenase in the liver
produces retinal (used in vision process) which is reduced to retinol
(vitamin A1 below)
• Any carotenoid with an unsubstituted b-ring works
• Carotenoids are absorbed more efficiently from cooked foods than
fresh
• Retinol and its derivatives are found only in animal products – these
provide some of our dietary needs. Cod-liver oil and halibut-liver oil
are rich sources
• Many xanthophylls also absorbed by human body, though not the
epoxyxanthophylls (e.g. neoxanthin)

09/08/2023 TERPENES 41
 Carotenoids provide color (attractants)
• Carotenoids, together with chlorophylls and
anthocyanins, give most natural food colors
• b-carotene is most plentiful in green plant tissues,
followed by lutein & violaxanthin

09/08/2023 TERPENES 42
 Carotenoids in nature, cont’d
• Invertebrates often contain protein-associated carotenoids that
give green, blue, purple, gray coloration
• e.g. exoskeletons, eggs of crustaceans
• role: protective coloring for camouflage
• in plants, carotenoids act as light-harvesting pigments and
protect against photo-damage by scavenging peroxyl and
singlet oxygen
• plastids contain chlorophyll-carotenoid-protein complexes
(photosystems) to collect light energy for photosynthesis
• with ripening, chloroplasts turn to chromoplasts,
forming lipid-associated carotenoids
(plastoglobules) with structure changes
that result in color change
09/08/2023 TERPENES 43
 Around one in two million lobsters is blue. A research study conducted by
Professor Ronald Christensen at the University of Connecticut discovered
that a genetic defect causes a blue lobster to produce an excessive amount of
protein.[5] The protein, and a red carotenoid molecule known as astaxanthin,
combine to form a blue complex known as crustacyanin, giving the lobster its
blue color.[6]
Dennis Hoey (May 4, 2005). "Professor finds key to rare lobster color".
MaineToday.com. http://travel.mainetoday.com/news/050404blue.shtml .

Cooking releases the free

carotenoid from the protein,
turning the lobster red!

09/08/2023 TERPENES 44
 Carotenoid Esters:
• Carotenoids in fruits and flowers may be esterified
with fatty acids (e.g. lutein dipalmitate)
• This occurs especially during ripening, altering
solubility & polarity properties

09/08/2023 TERPENES 45
09/08/2023 TERPENES 46
09/08/2023 TERPENES 47
09/08/2023 TERPENES 48
09/08/2023 TERPENES 49
09/08/2023 TERPENES 50
09/08/2023 TERPENES 51
09/08/2023 TERPENES 52
09/08/2023 TERPENES 53
09/08/2023 TERPENES 54
09/08/2023 TERPENES 55
09/08/2023 TERPENES 56
 b-Carotene

09/08/2023 TERPENES 57
 Vitamin A

09/08/2023 TERPENES 58
 End-groups of Carotenoids

18' 4'
19 20 5' 3'
17 16
1 7 11 15 14' 12' 10' 8'
13' 9' 6' 2'
2 9 13
6 8 10 12 14 15' 11' 7' 1'
5 16'
3 17'
20' 19'
4 18

1
7 1
8

1 3 5
R
1
6 2 4 6

y-end group

09/08/2023 TERPENES 59
 Vitamin A and Beta-Carotene
• Also known as retinol, retinal, retinoic acid
• Vitamin A is found in the body in compounds known as
retinoids: retinol, retinal, and retinoic acid.
• These have functional roles in vision, healthy epithelial
cells, and growth.
• Vitamin A deficiency is a major health problem in the
world.
• Toxicity is often associated with abuse of supplements.
• Plant foods provide carotenoids, such as beta-carotene,
some of which have vitamin A activity.
• Animal foods provide compounds that are easily converted
to retinol.
• Retinol binding protein (RBP) allows vitamin A to be
transported throughout the body.
09/08/2023 60
TERPENES
09/08/2023 61
TERPENES
 Vitamin A and Beta-Carotene

• Roles in the Body

Vitamin A in Vision
• Helps to maintain the cornea
• Conversion of light energy into nerve impulses at
the retina
• Rhodopsin is a light-sensitive pigment of the retina
that contains a protein called opsin.

09/08/2023 62
TERPENES
09/08/2023 63
TERPENES
 Vitamin A and Beta-Carotene
• Roles in the Body
Vitamin A in Protein Synthesis and Cell
Differentiation
• Through cell differentiation, vitamin A allows
cells to perform specific functions.
• Epithelial cells
– Epithelial tissues on the outside of the body form
the skin.
– Epithelial tissues on the inside of the body form the
mucous membranes.

09/08/2023 64
TERPENES
09/08/2023 65
TERPENES
 Without vitamin A, the
Vitamin A maintains
normal structure and
healthy cells in the
function of the cells in
mucous membranes.
the mucous membranes
are impaired.

Mucus Goblet cells

09/08/2023 TERPENES 66
 Vitamin A and Beta-Carotene
• Roles in the Body
Vitamin A in Reproduction and Growth
• Sperm development in men
• Normal fetal development in women
• Growth in children
• Remodeling of the bone involves osteclasts,
osteoblasts, and lysosomes.
– Osteoclasts are cells that destroy bone growth.
– Osteoblasts are cells that build bones.
– Lysosomes are sacs of degradative enzymes that destroy
bones.

09/08/2023 67
TERPENES
 Vitamin A and Beta-Carotene

• Roles in the Body

Beta-Carotene as an Antioxidant
• Beta-carotene helps protect the body from
diseases, including cancer.

09/08/2023 68
TERPENES
 Vitamin A and Beta-Carotene
• Vitamin A Deficiency
 Because vitamin A is stored in the body, it would take a
year or more to develop a deficiency in the presence of
inadequate intake.
 Infectious Diseases
• Impaired immunity correlates with vitamin A deficiency in
children.
• The goals of worldwide health organizations include vitamin A
supplementation.
 Night Blindness
• First detectable sign of vitamin A deficiency
• Inability to see in dim light or inability to recover sight after a
flash of bright light

09/08/2023 69
TERPENES
09/08/2023 70
TERPENES
 Vitamin A and Beta-Carotene
• Vitamin A Deficiency
Blindness
• Xerophthalmia is blindness due to vitamin A
deficiency.
• Xerosis is the first stage where the cornea becomes
dry and hard.
• Keratomalacia is the softening of the cornea.
Keratinization
• Epithelial cells secrete a protein called keratin—the
hard, inflexible protein of hair and nails.
• Changes in epithelial cells results in keratinization,
rough, dry and scaly skin.
Deficiency disease is called hypovitaminosis A
09/08/2023 71
TERPENES
09/08/2023 72
TERPENES