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Terpenoids
Terpenoids
DESTA S.
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Terpenes
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What are terpenes?
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Essential oils contain terpenes
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Spices contain terpenes
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Terpenes are unsaturated
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Isoprene
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H2C C CH CH2 C CH
H2C
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Isoprene
8
Head Tail
CH3 CH2
C CH =
CH2
Isoprene
(2-methylbuta-1,3-diene)
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Myrcene – a linear terpene
10
C CH C CH C
C CH
CH
H3C CH2
C
CH
H2C CH2
H2C CH
C
CH3
Limonene
(skin of citrus fruits)
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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)
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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)
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Camphor – a cyclic terpenoid
CH3
H3C
C
CH
CH2 CH2
C
H2C C
H3C
O
Camphor
(Camphor tree)
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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
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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
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TERPENS
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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.
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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.
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monoterpenes
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sesquiterpenes triterpene
diterpene
tetraterpenes
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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.
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Questions
Which unit makes up every terpene?
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Carotenoids
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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)
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Biosynthesis:
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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
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(peppers)
34
on
m m
rsi
pe
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Some common carotenoids with cyclic end
structures:
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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 .
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
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b-Carotene
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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.
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Vitamin A and Beta-Carotene
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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.
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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.
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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.
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Vitamin A and Beta-Carotene
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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
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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
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