Dr. Md. Rageeb Md.

Usman
Associate Professor
Department of Pharmacognosy

Smt. Sharadchandrika Suresh Patil

College of Pharmacy,
Chopda, Maharashtra, India
 INTRODUCTION
 HISTORY
 MONOTERPENES
ACYCLIC MONOTERPENES
MONOCYCLIC MONOTERPENES
BICYCLIC MONOTERPENES
 SESQUITERPENES
Acyclic compounds
Cyclic compounds
 DITERPENES
 SESTERPENES
 TRITERPENOIDS
 HYDROCARBONS
ALKANES, ALKENES
CYCLIC HYDROCARBONS
CAROTENOIDS
 RUBBER
 Terpenoids (isoprenoids), a subclass of the
prenyllipids (terpenes, prenylquinones, and
sterols), represent the oldest group of small
molecular products synthesized by plants.
 During the 19th century, chemical works on
turpentine led to name "terpene" the
hydrocarbons with the general formula
C10H16 found in that complex plant product.
These terpenes are frequently found in plant
essential oils.
 They are universally present in small amounts in
living organisms, where they play numerous
vital roles in plant physiology as well as
important functions in all cellular membranes.
 They may be defined as a group of molecules
whose structure is based on a various but
definite number of isoprene units (methylbuta-
1,3-diene, named hemiterpene, with 5 carbon
atoms).
 Terpenoids are
extraordinarily diverse
but they all originate
through the
condensation of the
universal
phosphorylated
derivative of
hemiterpene,
isopentenyl diphosphate
(IPP) and dimethylallyl
diphosphate (DMAPP)
giving geranyl
pyrophosphate (GPP).
 Terpenes are hydrocarbons resulting from the
combination of several isoprene units. modified
terpenes.
 according to the number of isoprene units used:
 Hemiterpenoids, 1 isoprene unit (5 carbons)
 Monoterpenoids, 2 isoprene units (10C)
 Sesquiterpenoids, 3 isoprene units (15C)
 Diterpenoids, 4 isoprene units (20C)
 Sesterterpenoids, 5 isoprene units (25C)
 Triterpenoids, 6 isoprene units (30C)
 Tetraterpenoids, 8 isoprene units (40C)
 Polyterpenoid with a larger number of isoprene
units
 Terpenoids can also be classified according to the
number of cyclic structures they contain.
 Mono-, Sesqui-, Di-, And Sesterpenes contain
the isoprene units linked in a head to tail
fashion. The triterpenes and carotenoids
(tetraterpenes) contain two C15 and C20 units
respectively linked head to head.
 Many terpenes are hydrocarbons, but oxygen-
containing compounds such as alcohols,
aldehydes or ketones are also found. These
derivatives are frequently named terpenoids.
 Mono- and sesquiterpenes are the chief
constituents of the essential oils while the other
terpenes are constituents of balsams, resins,
waxes, and rubber.
 Oleoresin is a roughly equal mixture of
turpentine (85% C10-monoterpenes and 15%
C15- sesquiterpenes) and rosin (C20-diterpene)
that acts in many conifer species to seal wounds
and is toxic to both invading insects and their
pathogenic fungi.
A number of inducible terpenoid defensive
compounds (phytoalexins) from angiosperm
species are well known. These include both
sesquiterpenoid and diterpenoid types.
 Terpenes history spans various civilizations. As they
are largely found in essential oils, they were used in
the Ancient Egypt for various religions aims.
 Camphor was introduced in Europe from the East by
the Arabs around the 11th century.
 The process of obtaining plant essential oils by fatty
extraction was known by the early Middle Ages. In
the 12th century, Arnaud de Villanosa described
distillation of oils from rosemary and sage. He made
an "oleum mirabile" from oils of turpentine and
rosemary. It is noticeable that some 60 oils were
described in the Nuremberg edition of
"Dispensatorium valerii cordi" written in 1592.
 Analyses of oils of turpentine were made in 1818 by
JJ Houston de la Billardière.
 Dumas proposed in 1866 the name "terpene",
derived from turpentine, instead of camphor for
crystalline oxygenated substances extracted from
essential oils. In 1887,
 Wallach O proposed that one isoprenic unit of 5
carbon atoms (C5H8) is always present in the
molecule of terpenes.
 The structure of camphor was established by Bredt
in 1893, that of pinene by Wagner in 1894 and that
of citral by Tiemann in 1895.
 b-Carotene was isolated in 1837 by Wackenrodder
from carrots, and its correct molecular form was
determined in 1907 by Willstätter.
 The period since 1945 has seen an extensive explosion
in natural product chemistry due to the advent of
chromatographic and spectroscopic techniques. The
discovery of the isoprene unit is the basis of the concept
of the "isoprenic rule" edicted in 1953 by Ruzicka L and
completed by Lynen F et al. and Bloch K et al.
 Mevalonic acid was shown in 1956 to be a biosynthetic
precursor of cholesterol and later, its incorporation into
a number of terpenoids has been demonstrated.
Actually, an increasing number of terpenoids are
described in the plant kingdom and many of them were
shown to have important biological activities.
 Thus, several sesquiterpenes and diterpenes have
antibiotic properties, some sesquiterpenes and
diterpenes are insect and plant hormones, respectively.
 They are the terpenes that have been known for
several centuries as components of the fragrant
oils obtained from leaves, flowers and fruits.
 Monoterpenes, with sesquiterpenes, are the
main constituents of essential oils.
 While a few, such as camphor, occur in a near
pure form, most occur as complex mixtures,
often of isomers difficult to separate.
 These essential oils have numerous actions,
such as allelochemical functions between plants
and between plants and predators.
 A role in wound healing was also observed.
 They can be
considered as
derivatives of 2,6-
dimethyloctane.
 Among natural
molecules, the
followings are well
known and have
several structural
isomers.
 A great number of orchid species in the New
World tropics have coevolved with the insects
Euglossini by producing floral scents, highly
attractive to insect males over great distances,
for efficient pollination.
 Ipsdienol has been shown to be the main
attractive component of the orchid scent.
 Ipsdienol
 They are derived from cyclohexane with an
isopropyl substituent.
 Limonene is an important volatile emitted by the
holm oak, and acts as allelochemical in
inhibiting seed germination of other plant
species.
 Thuyone is best
known for being a
toxic chemical in
absinthe, a product
extract from Artemisia
absinthium.
 Its psychedelic effects
consecutive to
absinthe consumption
is disputed.
 Pharmacologically,
thujone acts mainly on
the GABA receptors in
the brain and exhibits
psychoactive
response.
 Pinene is, as limonene,
an allelochemichal
emitted by the roots
of Quercus ilex.
 Camphor and pinene
are also
allelochemicals emitted
by Salvia leucophylla .
 Iridoids are a class of
bicyclic monoterpenes
found in a wide variety
of plants and in some
animals.
 Iridoids are typically found in plants as
glycosides, most often bound to glucose.
 Cleavage of a bond in the cyclopentane ring
gives rise to a subclass known as seco-iridoids.
 Isolated and purified, iridoids exhibit a wide
range of bioactivities including cardiovascular,
hypoglycemic, anti-inflammatory,
antispasmodic, antitumor, antiviral,
immunomodulator and purgative activities.
 They are produced by plants primarily as a defense
against herbivores or against infection by
microorganisms.
 To humans and other mammals, they have also a
deterrent bitter taste.
 It can also be used as a mosquito repellent.
 As other terpenes, iridoids may function as
protective substances in the animal kingdom,
especially for insects.
 Many monoterpenes possess antitumor activity in
animal and cell models.
 They have also antioxidant properties, g-terpene
and hydroxytyrosol being among the most effective.
 Sesquiterpenoids are defined as the group of 15
carbon compounds derived by the assembly of 3
isoprenoid units and they are found mainly in
higher plants but also in invertebrates.
 Sesquiterpenes, with monoterpenes, are an
important constituent of essential oils in plants.
 They are the most diverse group of isoprenoids.
 In plants, they function as pheromones and
juvenile hormones.
 Sesquiterpene structures present several acyclic,
mono-, bi-, tri-, and tetracyclic systems.
 The acyclic
representative are
also called farnesans,
term derived from
the basic structure,
farnesol.
 Farnesol and
nerolidol are very
common and are
isolated from
essential oils of
various sources.
 Farnesol is widely distributed in many essential oils such
as citronella, neroli, cyclamen, lemon grass, tuberose,
rose, musk, and balsam.
 It is used in perfumery to emphasize the odors of
perfumes.
 Moreover, it is a natural pesticide for mites and is also a
pheromone for several insects and mammals, including
elephants.
 Farnesol was also show to be the “quorum-sensing
molecule” identified in fungi.
 The presence of farnesol prevents the yeast-to-
mycelium conversion, resulting in actively budding
yeasts without influencing cellular growth rates.
 This study is the first to identify an extracellular
molecule mediating an eukaryotic quorum-sensing
system.
 Farnesol is active against a variety of Candida albicans at
concentrations between 1 and 50 mM.
 Farnesol is frequently esterified with one fatty acid
having 8 to 12 carbon atoms.
 Farnesene, an analogue of farnesol, is known to act as
an alarm pheromone in aphids.
 Released during predator attack, it causes aphids to
stop feeding, disperse, and give birth to winged (rather
than wingless) forms, which leave their host plants.
 Farnesene is produced by de novo biosynthesis by
cotton plants when damaged by insect herbivories.
 These compounds likely mediate the interaction between
herbivores and their natural enemies, attracted by
terpenes.ing 8 to 12 carbon atoms.
Farnesene
 Nerolidol is present in neroli, ginger, jasmine,
lavender, tea tree and lemon grass.
 The aroma of nerolidol is woody and
reminiscent of fresh bark.
 It is used as a flavoring agent and in perfumery.
 It was also shown to be produced by the leaves
of a large number of plant species in response
to herbivory insects and then to be transformed
into a C11-homoterpene (4,8-dimethyl-1,3,7-
nonatriene) which attracts predatory insects.
4,8-Dimethyl-1,3,7-nonatriene
 Among the acyclic species, two compounds are well
known for their importance in invertebrate
endocrinology.
 One, methyl farnesoate is now considered as the
crustacean juvenile hormone and is synthesized by the
mandibular organs and is present in the hemolymph.
 Its structure is nearly identical to the other one, the
insect juvenile hormone III which regulates
metamorphosis and reproduction. Both are synthesized
from farnesoic acid in the corpora allata.
 Farnesoic acid has been determined to be the
autoregulatory substance involved in the regulation of
the morphological transition of the yeast Candida
albicans between a budding form and a multicellular
invasive filamentous form.
 This transformation has been postulated to
contribute to the virulence of this organism.
These findings might have medicinal value in
the development of anti-fungal therapies.
 Abscisic acid plays a key role in
plants in the regulation of stomatal
closure by regulating ion channel
activities and water exchanges across
the plasma membrane of guard
cells.
 Cyclic ADP-ribose (cADPR) has been
shown to mediate signaling of
abscisic acid in the drought-stress
response leading to activation of
gene transcription and to stomatal
closure.
 It was shown that diacylglycerol
pyrophosphate plays a role as
phospholipid second messenger in
abscisic signaling.
 Abscisic acid is not restricted to the plant kingdom
and primitive invertebrates since it has been shown
to be present in the central nervous system of pigs
and rats.
 Evidence was provided that it is also involved in the
stimulation of human granulocytes with cyclic ADP-
ribose as second messenger.
 This lipid may be considered as a new pro-
inflammatory cytokine in humans.
 Human granulocytes and smooth muscle cells are
also functionally activated by abscissic acid.
 That messenger can be considered as a new signal
molecule involved in the development of
atherosclerosis.
 Abscisic acid was shown to be a endogenous stimulator
of insulin release from human pancreatic b cells with
cyclic ADP-ribose as second messenger.
 This observation suggests that this lipid phytohormone
may be involved in the physiology of insulin release,
mainly in its dysregulation under conditions of
inflammation.
 Together with jasmonates, abscisic acid was shown to
control excitability and closure of the insect trap
of Dionaea muscipula (Venus flytrap).
 Cadalene has the cadinane skeleton and is present in
essential oils and in many plants.
 It is used as a biomarker in paleobotanic studies.
 In connection with retene (1-methyl-7-isopropyl
phenanthrene), it enables the estimation in sediments of
the importance of Pinaceae in ancient forests.
 The function of curcumene as insecticide, repellent, and
insect feeding deterrent has been previously reported.
 A parent compound, bisabolol, isolated from essential
oils of a variety of plants, showed at low concentration a
differentiating effect in endothelial cells but an apoptotic
effect at higher concentration.
 Gossypol, a sesquiterpene dimer found in cotton that is
formed from two cadinane units.
 All the cotton plant contains gossypol.
 That terpene occurs as a mixture of two enantiomers but
each has different biological activities.
 For nonruminant animals (rodents, chickens, humans), (–
)-gossypol is significantly more toxic than the (+)
enantiomer. It has anti-cancer properties and inhibits
male fertility in humans. In contrast, cotton plants
containing high levels of (+)-gossypol are resistant to
insect damage. These terpenes must be removed from
the plant parts and oil before use as animal foods.
 Bicyclic sesquiterpenes with
a driman unit are
widespread in plants,
liveworts, fungi and certain
marine organisms
(sponges).
 Some drimanes have been
identified in petroleum and
are probably derived from a
microbial source.
 They have generally potent
antibacterial and antifungal
activities, and they are toxic Driman squeleton
to several invertebrates and
also in fish. In addition, they
deter feeding by insects on
plants and by fish on
sponges.
 Capsidiol is a
sesquiterpenoid
compound that
accumulates in
tobacco Nicotiana
tabacum and chili
pepper Capsicum
annuum in response to
fungal infection. It is
considered as a
phytoalexin. Capsidiol
 Avarol, and its quinone derivative
avarone, are biologically active
sesquiterpenoids which exhibited
antimicrobial and antifungal
activities and also active against
AIDS virus. They were isolated from
a Mediterranean (Dysidia avara) and
an Australian sponge (Dysidia spp).
 They have also potent antileukemic
activity both in vitro and in vivo in
mice.
 The 1,4-benzoquinone moietylinked
to the sesquiterpene is a common
structural feature in a large number
of terpenoid compounds which have
a large spectrum of biological
activities.
 Besides avarol, several other natural
quinones and hydroquinones, such
as illimaquinone, nakijiquinone and
bolinaquinone, are present in
Avarol
sponges of the order Dictyoceratida.
 All have cytotoxic and
antiproliferative properties
which offer promising opportunities
for the development of new
antitumor agents.
 Rasmann E et al.
discovered that insect-
induced (E)-b-
caryophyllene emission
from maize roots attracts
nematodes that prey on
the attacking insect
larvae.

(E)-b-Caryophyllene
 They have 20 carbon atoms and are derived
from geranylgeraniol pyrophosphate.
 They are of fungal or plant origin and are found in resins,
gummy exudates, and in the resinous high-boiling fractions
remaining after distillation of essential oils.
 The rosin remaining after distilling pine turpentine, for
instance, is rich in diterpenoids.
 In ancient times, conifer exudates were used for caulking
boats and waterproofing ropes.
 Resin secretion is also recognized to be part of the resistance
mechanism conifers employ against bark beetles and their
associated pathogenic fungi. Diterpenoid groups that are
physiologically active include: vitamin A activity (retinol),
phytohormones that regulate plant growth and germination,
e.g. gibberellin,
 fungal hormones that stimulate the switch from asexual to
sexual reproduction, e.g. trisporic acid; disease resistance
agents (phytoalexins), e.g. casbene and podocarpic acid, the
anticancer drug, taxol, from the bark of the yew tree, the
cancer promoter, phorbol, and natural cannabinoids.
 The diterpenes have
exceptionally open
chain, as found in
geranylgeraniol
or phytol which forms a
part of chlorophyll and
the side chain of
vitamin E and K,
and crocetin which is a
diacid diterpenoid and
the lipid part of the
crocins, glycosylated
derivatives present in
saffron.
Examples of diterpene
substances are given
adjacent n below :
 Abietic acid is an irritant
compound present in pine
wood and resin.
 It is the most abundant
compound present in rosin, the
solid fraction of the oleoresin
of coniferous trees.
 It is mainly used to make
lacquers and varnishes and
metal resinates.
 These resinates are produced
in reacting abietic acid (or a
similar compound) with a metal
salt (gold, indium, nickel,
palladium, platinum, silver ...)
and used in a wide variety of
applications where high purity
metals in organic solution form
is needed (gravure printing Abietic acid
inks, vitrifiable colors,
antifouling agent, dryers for
paints and varnishes ...).
 Steviol is the aglycone
of stevia's sweet glycosides,
one of them being formed
by replacing one hydrogen
atom (bottom) with glucose
via an ester link, and
another hydrogen atom (top)
with a disaccharide (glucose
and rhamnose).
 The steviol glycosides are
responsible for the sweet
taste of the leaves of
the stevia plant (Stevia
rebaudiana, Asteraceae).
Steviol
 These compounds are 40 to
300 times sweeter than
sucrose. They are developed
to be used in sweet drinks.
 Retene is present in tars
obtained by distillation of
resinous wood, it is an
important pollutant
eliminated by the paper
factories.
 This diterpene is present
in geological sediment
where it is formed by
diagenesis from abietic
acid, several intermediates
having been recognized.
 Thus, with cadalene
(sesquiterpene), retene, Retene
whichnis a diterpenoid
dehydrogenation product,
is used in paleobotanic to
estimate the importance of
ancient pine forests.
 Gibberellins are a family of compounds, over
130 members exist whose structures and
occurrence can be found on the web.
 The most important in plants is gibberellin A1
which is responsible for stem elongation.
 The most widely available compound is
gibberellic acid (one double bond in the right
cycle).
 Among the physiological properties,
gibberellins are involved in stem growth, seed
germination and fruit setting and growth.
 Dehydroleucodine
was isolated
from Artemisia
douglasiana, a
popular medicine in
Argentina and was
shown to have several
physiological and
therapeutic properties
: anti-proliferative
activity in G2 phase,
cytoprotective agent
for gastric ulcers and
a general antioxidant.
 Cafestol and kahweol are
present in high
concentrations (up to 18%
diterpene esters) in the oil
derived from coffee beans.
 The only difference between
cafestol and kahweol is an
extra double bond present
in the second cycle of
kahweol.
 These diterpenes are
esterified with one fatty acid
(C14 to C24), palmitic and
linoleic acids being the
major esterified fatty acids.
 Terpenes were also shown
to induce an elevated
plasma cholesterol content
in human.
 Phorbol is a diterpene
isolated in 1934 from
croton oil (seeds of Croton
tiglium).
 Various fatty acid esters of
phorbol have important
biological properties, the
most notable of which is
the capacity to act as
tumor promoters through
activation of protein
kinase C as they mimic
diacylglycerols.
 The most common
Phorbol
phorbol ester is phorbol-
12-myristate-13-acetate R : myristic acid (C14:0),
(PMA), which is used as a Ac : acetate group
research tool in models of
carcinogenesis.
 Cannabinoids are a group of
diterpenes present in
Cannabis (Cannabis sativa L).
 All these substances are
structurally related to
tetrahydrocannabinol (THC)
and are able to bind to
specific cannabinoid
receptors.
 Tetrahydrocannabinol, also
known as Δ9-THC or Δ9-
tetrahydrocannabinol, is the
main psychoactive substance Δ9-Tetrahydrocannabinol (THC)
found in the plant.
 It was isolated by
Mechoulam R et al. in 1964.
 They are derived
from geranylfarnesol pyrophosphate and have
25 carbon atoms. They were isolated from insect
protective waxes and from fungal sources.
 Three examples of sesterpenes are shown below.
 Variously unsaturated and
branched sesterpenes,
known as Haslenes, were
found in species of
diatomaceous algae.
 They are widely
distributed and abundant
in marine sediments.
Several haslenes were
found to be produced by a
pennate diaton Haslea
ostrearia according to the
culture temperature and
were shown to have
cytostatic properties.
 One of them is shown
below.
 They form a large group of natural
substances which includes steroids and
consequently sterols.
 Squalene is the immediate biological
precursor of all triterpenoids.
 Biochemistry, molecular biology, and
applications of squalene have been reviewed.
 Squalene epoxide (2,3-
oxidosqualene) is produced by the
enzyme squalene epoxidase which
use NADPH and oxygen to oxidize
squalene.
 This metabolic step is the first
in sterol Squalane is a completely
saturated derivative of squalene.
Present in sebum, it is largely used
as a component in many cosmetic
products.
 It is obtained by hydrogenation of
squalene extracted from olive oil.
 The large group of steroids,
including sterols, are present in
very small amounts in bacteria but
at larger amounts in plants and
animals while the hopanoids are
very abundant in prokaryotes
where they replace cholesterol.
Squalene epoxide
biosynthesis leading to the
formation of lanosterol or
cycloartenol.
 Among the large number of triterpenoid
structures, some of them are shown below.
 Steroids are modified triterpenes which derived
also from squalene by cyclization, unsaturation
and substitution.
 The nucleus of all steroids is the tetracyclic C17
hydrocarbon 1,2-
cyclopentanoperhydrophenanthrene (gonane or
sterane) substituted by methyl groups at C10
and C13, as well as an alkyl side-chain at C17.
 Steroids may possess a nucleus derived from the
former one by one or more C-C bond scissions
or ring expansions or contractions.
Gonane and three examples of basic
unsubstituted steroids are shown below.
 Unsaturated steroids with most of the skeleton
of cholestane containing a 3b-hydroxyl group
and an aliphatic side chain of 8 or more carbon
atoms attached to position 17 form the group of
sterols.
 The hopanoids are pentacyclic triterpenoids based on
the hopane skeleton (with a five-membered ring
E) are widely distributed in prokaryotes but were not
detected in Archaea.
 In most cases, the hopanoid content of the cell is
comparable with the cholesterol content of
eukaryotic cells.
 They are considered as membrane rigidifiers.
 Furthermore, they are the precursors of several
derived compounds (homohopanoids) in sediments
and oils and thus could be considered as the most
abundant natural products on earth.
 Although oxygen is not required for hopanoid
biosynthesis, the vast majority of known hopanoid
producers are aerobic or micro-aerophilic bacteria.
 Thus, hopanoids are found predominantly in aerobic
methanotrophs, heterotrophs and cyanobacteria, but
have also been found in some anaerobic bacteria.
 The simplest C30 hopanoid is diploptene.
 Cyanobacteria are presently the only known
bacteria to synthesize abundant 2-
methylhopanoids with an extended
polyhydroxylated side chain.
 The most abundant hopanoids are C35
bacteriohopanepolyols in which the side-chain
of the parent structure contains a variable
number of vicinal hydroxyl
groupsThe hopanoids are widely distributed in
bacteria and blue-green algae where they are
important cell membrane constituents.
 It is often said that hopanoids are the "most
abundant natural products on Earth".
 As hopanoids are very stable and are not easily
degraded, they are receiving an intense attention
as biological markers with applications for
geochemical studies of petroleum source rocks and
oils.
 These biomarkers are mainly derived from bacterial
bacteriohopanepolyols (biohopanoids).
 The 2-methylhopane derivatives are abundant in
organic-rich sediments as old as 2,500Myr.
 These lipids may help constrain the age of the
oldest cyanobacteria and the advent of oxygenic
photosynthesis. They could also be used to quantify
the ecological importance of cyanobacteria through
geological time.
 More recent investigations have shown that the
production of substantial quantities of
polyhydroxylated 2-methylhopanoids may occur in
phototrophs other than cyanobacteria and that their
biosynthesis does not require molecular oxygen.
 Aminohopanoids not very
different from the previous
one have been identified in
several methylotrophic
bacteria.
 One of the most abundant is a
aminohopane pentol, mixed
with other parent compounds
(triol and tetrol).
 This C30 aminopentol is a
possible precursor of the
widespread C29 hopanoid
chemical fossils.
 Different bacterial groups
possess recognizable
biohopanoid distributions,
giving hopanoids marker
potential for specific bacterial
populations and Aminobacteriohopane
environmental conditions.
 More than 150 individual
hopane derivatives have been
isolated from various types of
sedimentary organic matter.
 Other pentacyclic
triterpenoids based on
the lupane skeleton
include a very large
number of naturally
occurring members
with different functional
groups which are found
in vegetables and fruit.
 Among them, lupeol is
one of the most
ubiquitous
compounds.
 Lupeol was shown to have
various pharmacological
properties, inducing anti-
inflammatory and anti-
arthritic responses and
inhibition of tumor growth in
animal cells.
 Long-chain fatty acid esters
(C20, C22 and C26) of lupeol
extracted from an African
plant,Holarrhena
floribunda (Apocynaceae),
were shown to have strong
antimalarial activity, especially
against drug-resistant strains
of Plasmodium falciparum.
 Fatty acid esters (palmitic or Palmitic acid ester of lupeol (Procrim a)
stearic acid) of lupeol have
been isolated from green
propolis produced by
honeybees from vegetative
apices of the
Asteraceae Baccharis
dracunculifoliafrom Brazil.
 These compounds were
named procrim a and b.
 Ursolic acid is present in
numerous plants and is the
best known triterpene from the
ursane group.
 It amounts at more than 1 g
per 100 g dry weight
in Thymus, Rosmarinus, Salvia,
Lavandula, and Eucalyptus.
 It is found at high
concentration in coffee seeds
and in apple fruit.
 It is used in cosmetics as an
anti-inflammatory,
antibacterial and antifungal
drug.
 Ursolic acid is also able to Ursolic acid
inhibit some form of cancer,
particularly multiple myeloma.
 As ursolic acid but in contrast
with the hopane series, which
possesses a five-membered
ring E,
the gammacerane skeleton is
characterized by a six-
 Tetrahymanol (gammaceran-21a-
ol), a typical representative of the
series, was first isolated from the
ciliate protozoan Tetrahymena
pyriformis.
 Later, it was detected in a number
of other eukaryotes, e.g. in ferns,
fungi and some other ciliates.
 Its occurrence was long thought to
be restricted to eukaryotes but its
presence in sediments pointed out
a much more widespread
distribution in living organisms. T
 he finding of tetrahymanol in the
purple nonsulfur
bacterium Rhodopseudomonas
palustris opened new insights into
the biochemistry of these
molecules in bacteria.
 Tetrahymanol and novel
methylated homologues were
discovered in nitrogen-fixing
bacterium Bradyrhizobium
japonicum .
 Celastrol is a hopanoid
triterpene extracted from a
plant used in the Chinese
medicine, Tripterygium
wilfordii.
 That plant is useful to treat
inflammatory and
autoimmune diseases.
 New research have
demonstrated that it is a
potent proteasome inhibitor
and can help in the treatment
of prostate cancer.
 Its antioxidant and anti-
inflammatory properties has Celastrol
been the basis of research on
diseases induced by
monocytes and macrophages
activation, including
neurodegenerative process.
 These compounds form the simplest form of
lipids, they contain only carbon and hydrogen.
 They may be divided into aliphatic
hydrocarbons with a carbon chain which may be
linear (normal), branched, saturated (alkanes) or
unsaturated (alcenes), cyclic hydrocarbons and
carotenoids.
 Several hydrocarbons may be substituted with
oxygen-containing groups.
These organic compounds include :
ALKANES, ALKENES
CYCLIC HYDROCARBONS
CAROTENOIDS
 These molecules are found mainly in petroleum but living organisms,
eukaryotic or prokaryotic, contain frequently hydrocarbons which are directly
derived from fatty acids.
 They are known to be present in living matter since 1892 when Shall C
identified undecane in ants, and Etard A identified eicosane inBryonia dioica.
 They are distinct from the terpenoid hydrocarbons.
 They have usually a straight chain of up to about 36 carbon atoms but
may also be branched, with one or more methyl groups attached at almost
any point of the chain.
 Usually, the methyl group is near the end of the chain (iso or anteiso).
 They are either saturated or unsaturated (mono or diunsaturated).
 In contrast with the diversity of methyl-branched alkanes found in insect
species, n-alkanes predominate in plants.
 Among the least polar components of plant surface lipids hydrocarbons with
the odd number carbon chains (C15 up to C33) are predominant.
 Allenic hydrocarbons, such as 9,10-tricosadiene, 9,10-pentacosadiene, and
9,10-heptacosadiene were isolated from Australian insects (melolonthine
scarab beetles).
 Many microalgae contain the highly unsaturated
alkene n-C21:6 formed by decarboxylation of the
22:6n-3 fatty acid.
 A few species also contain the n-C21:5 alkene
(Volkman et al., Org Geochem 1994, 21, 407).
 Several microalgae were shown to contain long-
chain unsaturated alkenes from 19 to 38 carbon
atoms and one to four double bonds.
 Hydrocarbons are found at the outer surface in
higher plant leaves. As an example, C27, C29, and
C31 n-alkanes are the most abundant (from 11 to
19%) in needle wax of the Pinaceae Picea omorika .
 They are also abundant at the outer surface of
insects and several marine organism.
 They are thought to serve as a barrier to water
influx in the organism, to act as sex attractants (or
anti-aphrodisiacs), to affect the absorption of
chemicals and microorganisms.
 Wild populations ofDrosophila melanogaster use
several cuticular hydrocarbons (mainly 7,11-
heptacosene) as sexual pheromone.
 The roles of hydrocarbons in the recognition
systems of insects has been reviewed.
 Several hydrocarbons are produced as alarm
pheromones by the Dufour's gland in the ants.
 Five hydrocarbons have been described, undecane,
tridecane, pentadecane, 2-tridecanone, 2-
pentadecanone.
 During the act of stinging, formic acid and
hydrocarbons are discharged simultaneously from
these glands in fine droplets.
 These hydrocarbons act also as spreading agents for
 Cuticular hydrocarbons have proved to be useful for
identifying insect species and differentiating
populations.
 In combination with cuticular hydrocarbons,
isoprenoid soldier defensive secretions have been
used in some termite species for chemotaxonomic
analyses.
 Thus, analyses have shown that the hydrocarbon
profiles of French populations of subterranean
termites,
 Reticulitermes flavipes, were closer to termite
populations from Louisiana than to those from
Florida.
 Several hydrocarbons (octane, nonane, dodecane,
hexadecane...) belong to aroma compounds which
are found in environmental or food systems.
 Various hydrocarbons are present
in the photosynthetic prokaryotes
but in low concentrations.
 Most species have from 15 to 20
carbon atoms, heptadecane being
by far the most predominant in all
species.
 In some species, mono- or di-
unsaturated chains (alcenes) were
found, in others (Cyanobacteria)
methyl-branched alkanes are
present.
 Several alcenes with 8 or 11
carbon atoms and 3 or 4 double
bonds play a role in algae gamete
attraction (pheromones) :
cystophorene in Cystophora sp,
finavarrene in Ascophyllum sp
and Sphaerotrichia sp,
fucoserratene in the brown
seaweed Fucus serratus and in the
freshwater diatom Asterionella
formosa (Bacillariophyceae) .
 Hydrocarbons are also formed
as products of fatty acid
cleavage
during peroxidation processes.
Alkanes as well as alkenes
appear during hydroperoxide
decomposition.
 Among hydrocarbons, a variety
of forms are described
(saturated or unsaturated):
 The normal paraffins : their
general formula is
CH3(CH2)nCH3 (n= 6 - 40 or
greater).
Paraffins may have branched
chains :
 one methyl
group (monobranched), iso-
branched hydrocarbons (methyl
group on the second carbon)
or anteiso-
branched hydrocarbons (methyl
group on the third carbon)
 Among the almost 1,000 cuticular hydrocarbons
present in ant species, about 200
monomethylakanes and 600 dimethylakanes are
used for chemical communication.
 Odd chain lengths and positions of methyl at odd
carbon numbers are far more numerous than
even chain-length compounds.
 That chemical recognition, fundamental in insect
societies, is known for over 100 years in ants and
was shown to be based on antennal detection of
non-volatile compounds found on cuticle.
 Since 1987, the nest-mate discrimination
systems in several ant species are known to be
based on hydrocarbons.
 In longhorned beetle, Mallodon
dasystomus (Coleoptera, Cerambycidae), cuticular
hydrocarbon profiles of females contained 13
compounds that were not present in profiles of
males.
 Among the female-specific compounds, two co-
dominant methylbranched alkanes, 2-
methylhexacosane and 2- methyloctacosane, are
contact pheromes and accounted for 17% of the
total hydrocarbons.
 several methyl groups (multibranched), one for each
unit deriving from the isoprene formula :
CH2=C(CH3)-CH=CH2. Hydrocarbons formed of
isoprene units belong to the large group
of terpenes.
 This chain type is frequently found in several lipid forms,
either isolated or combined with other chemical
structures.
 A series of long-chain methylated alkanes (more than 23
carbon atoms), saturated or with one double bond, were
identified in settling particles and surface sediments
from Japanese lakes and were shown to be produced by
planktonic bacteria being thus useful molecular markers.
 Laboratory experiments have demonstrated that n-
alkanes up to C35 may be formed in the laboratory
under hydrothermal conditions (Fischer-Tropsch-type
reactions) from formic acid or oxalic acid.
 These results support the theory of the origin of life in
hydrothermal systems.
 It must be noticed that highly
branched and unsaturated (2-5 double
bonds) isoprenoids are widespread
components in marine sediments.
 The identification of C25 and even of
C30 highly branched isoprenoid
alkenes in diatoms have clearly
established that they are the source of
these compounds found in sediments.
 Among the saturated isoprenoids
found in geological sediments and oils,
the most frequent are
pristane (2,6,10,14-
tetramethylpentadecane)
and phytane (2,6,10,14-
tetramethylhexadecane).
 Both compounds can be generated
diagenetically from the phytol side
chain of chlorophyll.
 Pristane may also derive from the side
chain of tocopherols while phytane is
also generated by Archaea.
 The widespread use of pristane as a biological marker is
related to its structural similarity tophytol and its
apparent stability, in connection with inability of
microorganisms to carry out its anaerobic destruction.
 pristane is present in photosynthetic organisms, it has
been detected in bacteria, algae, and higher plants.
 Marine sources of pristane include zooplankton, lobster,
fish, sharks, sperm whale.
 Fossil fuels such as coal and petroleum contain this
compound.
 The stable structure persists even in Precambrian rocks
and perhaps in extraterrestrial meteorites.
 The coexistence of microfossils with pristane and
phytane in Precambrian rocks is significant to the
paleobotanist.
 Despite this inertness, pristane can be utilized as the
sole source of carbon and energy for growth of a
coryneform soil isolate.
 Crocetane is formed by four isoprene units arranged
symmetrically around a tail-to-tail linkage
(2,6,11,15-tetramethylhexadecane).
 It was initially synthesized and named by Karrer et
al..
 Crocetane is mainly present in oils and in methane-
rich sediments, as it was shown to be produced by
microorganisms utilizing methane as their carbon
source.
 2,6,10,15,19-Pentamethylicosane differs from
crocetane by the addition of a single isoprene unit,
joined head to tail, at one end of the molecule.
 This compound is present in methane-rich sediment
and is likely produced by anaerobic methanotrophs.
Phytane and biphytane, present in sediments and
petroleum, are thought to derive from ether-lipids
(archaeol, caldarchaeol) of Archaea, the only
organisms known to possess such structures.
 The separation of straight chain and branched
chain alkanes is efficient on a micro scale using
the urea complex formation as described
for fatty acids .
 That efficient method is based on the urea
inclusion directly on the TLC plates and
successive elutions with two solvents to
separate straight and branched alkanes.
 One important member of isoprenoid
polyenes is squalene (C30H50) which is
a metabolic precursor of sterols and
steroids and classified into
the triterpenoids.
 It is also a component of sebaceous
lipids (12-15% of sebum weight) found
on human skin.
 It consists of 6 isoprene units and
contains 6 trans double bonds. It was
discovered in 1906 in shark oil.
 It was suggested that squalene and its
peroxidized derivatives (6 are
possible) occurring by UV irradiation
have an important role in the
occurrence of sunburn, and/or
protection from sunburn skin damage.
 Furthermore, it has been suggested
that squalene peroxides may play an
important part in the pathology of
acne, pityriasis versicolor, and skin
aging.
 There is some evidence that squalene
reduces colon cancer and skin cancer.
 This activity is likely related to its
antioxidant effect.
 It must be mentioned that if squalene is found in large
quantities (from 0.2 to 0.9 g per Kg) in some fish liver
oils (shark), it is also found in olive oil (its content may
vary from 1 to 40 mg per Kg) where it is used to detect
any adulteration. Other vegetable oils contain only traces
of this compound (from 0.02 up to 0.3 mg per Kg).
 Squalene was also found in the epicuticular wax of fruit
(grapefruit) and in the hydrocarbon fraction of wheat.
 Squalene, and its saturated derivative (squalane) present
in skin sebum, are largely used in cosmetics.
 Squalane is obtained by hydrogenation of the squalene
pool isolated mainly from olive oil.
 It has been shown that
presqualene diphosphate,
intermediate between
farnesyl diphosphate and
squalene, carries biological
activity in human
neutrophiles and serves as
a negative intracellular
signal preventing
superoxide anion
generation.
 An inhibition of
phosphatidylinositol 3-
kinase in the same cells
was also demonstrated. Presqualene diphosphate
 During that signaling step,
squalene diphosphate is
transformed into the
inactive monophosphate
species.
 Two homologous series of trimethylalkanes, the
3,7,11-trimethylalkanes (C34H7), C36H74 and
C38H78) and the 4,8,12-trimethylalkanes (C35H72,
C37H76 and C39H80) have been described as the
major constituents of the cuticular alkanes of
the ant, Atta colombica.
 Each of these structures combines a reduced
polyketomethylene chain and a modified
isoprenoid chain, and hence combine structural
units from two major metabolic pathways.
 Hydrocarbons of this type have not been
previously isolated from natural sources.
 Hydrocarbons may be classified into
monocyclic species
and polycyclic species.
 Several branched-
alkylbenzenes have been
described in
Archaebacteria such
as Thermoplasma and Sul
folobus.
 They have mostly two
methyl groups branched
on a saturated chain of 9
to 12 carbon atoms.
 One of them is shown.
 After the first hypothesis
of a communication
system (chemotaxis) by
Thuret MG for the
fertilization of brown
algae, 117 years were
needed to know the
structure of the first algal
pheromone.
 This
compound, ectocarpene, is
an unsaturated heptacyclic
hydrocarbon found in the
brown
algae Ectocarpus, Adenocy
stis andSphacelaria.
 Several C11 alkylbenzenes similar to
ectocarpene play a role of pheromone in marine
brown algae, dityotene in Dictyota sp,
desmarestene in Desmarestia sp
and Cladostephus sp, lamoxirene
in Laminaria sp, Alaria sp and many others.

Alkylbenzenes from brown algae

 The C11-hydrocarbon ectocarpene was also
detected as component in the odor of ripening
mango but was also shown to be a metabolite in
leaves of the Asteraceae Senecio isatideus .
 Several biosynthetic studies suggest unsaturated
fatty acids as precursors of these pheromone
hydrocarbons.
 A review of hydrocarbon as chemical signals in
algal gamete attraction has been released.
 Several parent molecules (linear, tri-, penta- or
hexacyclic) with different degrees of
unsaturation and chain lengths have been
described in various algal species.
 The stilbenes (or
stilbenoids) form a group
of numerous compounds
based on a simple one,
stilbene.
 That compound consists
of two phenyl groups
linked by a trans ethene
double bond.
 Its name was derived
from the Greek word
"stilbos", which means
shining. Stilbene is
mainly used in trans-stilbene
manufacture of dyes and
optical brightening
agents.
 Stilbenes, sometimes classed into the
polyphenol group, are present in several vegetal
sources.
 Several forms have been described,
differentiated by various substitutions and
combinations of hydroxyl or alkoxyl groups.
 Some stilbenes are glycosylated. Thus, 2,3,5,4'-
tetrahydroxystilbene 2-O-b-D-glucoside, the
major bioactive compound from Polygonum
multiflorum, can efficiently inhibit the formation
of advanced glycation end products.
 Resveratrol (3,4',5-trihydroxystilbene) is
the most studied because of its
presence in grapes and wine and its
numerous pharmacological properties
(anti-cancer, antiviral, neuroprotective,
anti-aging, and anti-inflammatory).
Resveratrol
 It has been determined that resveratrol
is used by plants as a defensive
element.
 Thus, grape vine attacked by
mildew is able to product resveratrol
which can be transformed into
glycosylated or dimer compounds.
 The resistance of some cultivars seems
to be related to the toxicity of the
derivative.
 Similar observations were reported for
conifers. Resveratrol
 Pharmaceutic industries have developed
stilbene derivatives which have
estrogenic activity (non-steroidal
estrogens) such as diethyl stilbestrol.
 Diarylheptanoids belong to a compound group
having phenyl rings at 1,7 positions of n-heptane,
such as curcumin and several similar analogues
found in the rhizomes of the ginger (Curcuma
longa) family.
 Their common structure is shown below.

Diarylheptanoid
 Curcumin is the principal diarylheptanoid of the Indian spice turmeric,
which is a member of the ginger family (Zingiberaceae).
 That pigment, which gives the yellow color to turmeric (E100), was
isolated two centuries ago, and its structure as diferuloylmethane was
determined in 1910.
 Numerous therapeutic activities have been assigned to turmeric for a
wide variety of diseases and conditions, they are likely partly related
to its strong antioxidant properties.
 Plants of the Alnus genus (Betulaceae) have been found to be a
valuable source of diarylheptanoids similar to curcumin but with
various substituted chemical groups.
 Some of these compounds have valuable activities against LPS-
induced inflammation and could be the source of new anti-
inflammatory drugs.

Curcumin
 these hydrocarbons, whose only
few groups are present in plants,
may contain fused rings
containing only carbon or
heterocycles including foreign
atoms such as oxygen, nitrogen,
or several others.
 Polycyclic hydrocarbons
containing only carbon :
Naphthalene is a constituent of
Magnolia flowers.
 It may function as protection of
tissue against chewing insects
and it may attract insects to
pollinate by the UV absorption of
accumulated naphthalene in the Naphthalene
floral parts and floral scent.
 Naphthoquinones are
present in the secretion
of scent glands
of Opiliones .
 The two main
components which serve
chemical defense in
these animals are 1,4-
naphthoquinone and its
methylated derivative 6-
methyl-1,4-
naphthoquinone.
1,4-Naphthoquinone
 Binaphthyl compounds have been isolated from
the fungus (Ascomycetes) Daldinia concentrica.
One of them is shown below.
 Perylene is a typical
polyaromatic hydrocarbon
that occurs in many
sediments.
 Possible precursors include
binaphthyl compounds
derived from fungi, as those
cited above, in which case a
high abundance of
sedimentary perylene might
indicate a moist and humid
continental climate in the
depositional environment. Perylene
 New 9,10-dihydrophenanthrenes
and phenanthrenes were isolated
from Juncus setchuensis, a
plant which has long
been regarded as an antipyretic
and detumescence agent in
traditionalChinese medicine.
 Some of these compounds have
shown strong antitumor and
antialgal activities.
Many plants producing
phenanthrenes are used in
traditional medicine, likely in
connection with the cytotoxicity,
anti-microbial, spasmolytic, anti-
allergic, anti-inflammatory
activities of the natural
phenanthrenes present in these
plants. Denthyrsinin
 The anthracene nucleus
is present in several
compounds detected in
plants used in
traditional medicine.
 Thus, anthraquinone is
found in several plant
species (Aloes), fungi
and lichens but also in
insects where they play
Anthraquinone
a role of pheromone.
 Chrysophanol is a
member of the
anthraquinone family.
 Pharmaceutical studies
have shown that it exerts
a number of biological
effects, including
anticancer and
antimicrobial.
 The mechanism
underlying the anti-
inflammatory effects of
chrysophanol is likely
through the inhibition of
caspase-1. Chrysophanol
 Coumarins : the simplest compound of this group
is coumarin. Several others are coumarin derivatives by
various additions.
 It is found in many plants, notably in the tonka bean
from a tropical tree of the Fabaceae family (Dipteryx
odorata).
 It is produced also by the Poaceae vanilla grass
(Anthoxanthum odoratum) and buffalo grass (Hierochloe
odorata), and by a Rubiaceae plant, woodruff (Galium
odoratum).
 All these plants are strongly scented due to the presence
of coumarin which has been used in perfumes since
1882 (imitation of vanilla products).
 Coumarin, used as rodenticide, and extracts from these
plants are potential harmful as coumarin is the precursor
for several anticoagulants, notably warfarin.
 Some coumarin derivatives (phenylpropanoids) are
present in various plants. Among them, umbelliferone,
aesculetin, herniarin, psoralen and neoflavones.
 Scopoletin (6-methoxy-7-hydroxycoumarin) is a
phytoalexin produced by several Solanaceae, such as Coumarin
tobacco (Nicotania tabacum), which protects plants
against virus, bacteria or fungi.
 Osthole [7-methoxy-8-(3-
methylpent-2-enyl)coumarin]
is a coumarin derivative found
inCnidium monnieri, a plant
used in traditional Chinese
medicine to treat skin
affections. Osthole was shown
to exhibit several biological
functions, including
antiosteoporotic, antiallergic,
anti-inflammatory, and
antitumor functions.
 Recently, it was found that
osthole might be a potent Osthole
antidiabetic agent.
 Umbelliferone (or 7-hydroxycoumarin) occurs in many familiar
plants from the Umbelliferae family such as carrot or coriander
but also from other families such the Asteraceae Pilosella
officinarum.
 Umbelliferone absorbs ultraviolet light strongly but despite
possible harmful mutagenic properties, is used in sunscreens.
 An umbelliferone methoxylated derivative, herniarin (7-
methoxycoumarin) occurs in the leaves of tha Asteraceae water
hemp (Eupatorium ayapana) and in
several Herniaria (Caryophyllaceae).
 Psoralen (or psoralene) is a furanocoumarin. It is a derivative
from umbelliferone by addition of a furan ring.
 Psoralen has been described in the seeds of the
Fabaceae Psoralea corylifolia, but is present in many plants
such as several Rutaceae (Ruta, Citrus), Moraceae,
Leguminoseae (Psoralea, Coronilla) and Apiaceae. Psoralen-rich
plants are used in Chinese and Indian medicines and psoralene,
due to its UV absorption properties, is used in treatment of
psoriasis, eczema, vitiligo and in some cutaneous lymphoma.
 Many furanocoumarins are toxic and are
produced by plants as a defense
mechanism against various types of
predators and in human, some of them
(bergamottin) are responsible for the
"grapefruit juice effect", in which they
affect drug metabolism. They are also
bactericide, fungicide, antiviral and
insecticide and in plant they have an
important role as inhibitor of
germination.
 Butenolides are modified hydrocarbons
with a hetocyclic nucleus of the furan
type. The simplest one is 2-furanone.
 That compound is characteristic of aroma
of Apiacaea (genus Angelica). It can also
inhibit the quorum sensing in bacteria.
Several analogues or derivatives of 2-
furanone are present in fruit aroma : 4-
methoxy-2,5-dimethyl-3-furanone in
pineapple and 4-hydroxy-2,5-dimethyl-
3-furanone (furaneol) in strawberry and
tomato. Furaneol is present in roasted
peanut and tobacco smoke and 3,5,5’-
Furaneol
trimethyl-2-furanone appears in roasted 2-Furanone
in hazel-nut. Some other derivatives are
active as sexual pheromones in insects.
 Karrikins are a butenolide family of plant growth regulators found in smoke
derived from burning plant material (mainly cellulose).
 These compounds are derived from 2-furanone by condensation with a pyrane
group.
 They act as a key germination trigger for many species from fire-prone plants.
 It was later shown that karrikins act by a mechanism requiring gibberellic acid
synthesis and light. The most active karrikin is 3-methyl-2H-furo[2,3-c]pyran-
2-one (see below). Due to the fact that it has an effect at extremely low
concentrations (as low as 1 nM), it has potential as an important agronomic and
horticultural chemical.
 A parent compound (3,4,5-trimethylfuran-2-one) has been also isolated from
plant-derived smoke, but it has inversely a germination inhibiting property.
 Brominated furanones are produced by Delisea pulchra, a marine alga endemic to
the south-eastern coast of Australia.
 Some of which have strong inhibitory activity against fouling organisms and
herbivores. Additionally, furanones have specific effects on colonization
phenotypes of marine bacteria at concentrations found on the surface of the
alga. Manefield M et al. have shown that these compounds inhibit acylated
homoserine lactone-mediated gene expression in Escherichia coli.

Karrikin
 The core of quinolines is the
1-azanaphthalene nucleus.
The simplest one is quinolin.
 That compound is rarely
found in living material but
is present, as its derivatives,
in the plant Rutales and even
in some insects.
 Quinolin is also present in
some insects, as phasmids, Quinolin
where it plays a role against
predators.
 The bacteria Pseudomonas aeruginosa was shown to produce, besides
an alkyl homoserine lactone, new cell-to-cell signal molecules
(quorum sensing system).
 This molecule was determined to have a 4-quinolone base structure
with an alkyl chain (2-heptyl-3-hydroxy-4-quinolone) and therefore
has been designated as the Pseudomonas quinolone signal.
 Similar compounds have been previously described for their
antimicrobial activities.
 It was found that this molecule controlled the expression of genes
encoding for the major virulence factors.
 The maximal quinolone production occurs at the end of the
exponential growth phase, supporting the hypothesis that it acts as a
secondary regulatory signal for a subset of quorum sensing-controlled
genes.

2-Heptyl-3-hydroxy-4-
quinolone
 Later, another analogue was isolated from the same bacteria,
3,4-dihydroxy-2-heptylquinoline, which could be the direct
precursor of the previous quinolone and, likely, the message
molecule involved in cell-to-cell communication.
 A review of that type of quorum sensing may be read for further
information.
 In contrast with Pseudomonas quinolone, Burkholderia spp
produce several hydroxy-quinolines with a methyl group in
position 3 and a hydroxyl group in position 4 and various alkyl
chains.
 It was later shown that these quorum-sensing signals control the
bacterial synthesis of antibiotics.
 A new quinoline-2-carboxylic acid, 4-hydroxy-6-
methoxyquinoline-2-carboxylic acid (6-methoxy-kynurenic
acid), has been isolated from Ephedra pachyclada. Kynurenic and
6-hydroxykynurenic acids, previously reported from plants, were
also isolated from Ephedra .
 The nature of these compounds was discovered during the
19th century.
 In 1831, Wachen roder H. proposed the term "carotene" for
the hydrocarbon pigment he had cristallized from carrot
roots.
 Berzelius J. called the more polar yellow pigments extracted
from autumn leaves "xanthophylls" and Tswett M., who
separated many pigments by column chromatography, called
the whole group "carotenoids".
 Carotenoids consist of eight isoprenoid units joined in such a
manner that the arrangement of isoprenoid units is reversed
at the center of the molecule so that the two central methyl
groups are in a 1,6-position relationship and the remaining
non-terminal methyl groups are in a 1,5-position
relationship.
 They are, by far the predominant class of tetraterpenes. They
may be also classified in the terpenoids.
 Carotenoids can be considered derivatives of lycopene, found in
tomatoes, fruits and flowers.
 Its long straight chain is highly unsaturated and composed of two
identical units joined by a double bond between carbon 15 and 15'. Each
of these 20 carbon units may be considered to be derived from 4
isoprene units.
 Lycopene is a bioactive red colored pigment naturally occurring in
plants.
 Interest in lycopene is increasing due to increasing evidence proving its
antioxidant activities and its preventive properties toward numerous
diseases.
 In vitro, in vivo and ex vivo studies have demonstrated that lycopene-
rich foods are inversely associated to diseases such as cancers,
cardiovascular diseases, diabetes, and others.
 Carotenoids may be acyclic (seco-carotenoids) or cyclic (mono- or bi-,
alicyclic or aryl). Oxyfunctionalization of various carotenoids leads to a
large number of xanthophylls in which the function may be a hydroxyl,
methoxyl, carbonyl, oxo, formyl or epoxy group.
 Only some of the most common carotenes and xanthophylls are given
below:
 Phytoene is one of the first intermediates in the biosynthesis of
carotenoids.
 It is formed by coupling of two molecules of geranylgeranyl
pyrophosphate by the action of the phytoene synthase.
 The diphosphate is removed and proton shift leads to the formation of
phytoene. It is a colorless product and absorbs light in the UV range
only.
 Dietary phytoene is accumulated in human skin where it can potentially
protect the skin (UV absorber, antioxidant, anti inflammatory).
 Among the represented molecules, b-carotene is probably the most
important as a precursor of vitamin A by central cleavage into retinol and
some retinoic acid (b-carotene provides about 40% of human dietary
retinol equivalents).
 The majority of carotenoids are still manufactured chemically, but,
currently, the microbial production of b-carotene is of commercial
importance.Blakeslea trispora is one of the best fungal strain employed
for the production of b-carotene, commercially utilized by DSM. B.
trispora produces up to 3% carotene per cell dry weight.
 B. trispora is also employed for the production of natural lycopene,
commercialized by Vitatene. The marine algae Dunaliella salina is also
employed for manufacturing of b-carotene.
 In human serum several
carotenes and xanthophylls
have been detected.
 If a- , b-carotene and
lycopene are frequently
quoted in specialized papers,
some others are now
determined with precise HPLC
methods (lutein, zeaxanthin,
cantaxanthin and b-
cryptoxanthin).
 These compounds originate
from ingested fruit, green
leaves, berries and yellow
corn.
 Lutein has its maximum
absorption at 450 nm,
cryptoxanthin at 453 nm and
zeaxanthin at 454 nm. Xanthophylls
 Lutein and zeaxanthin are the only xanthophylls found in
human serum that are present in retina, macula (the
central region of the eye (they are frequently referred to
as macular pigment), and lenses. Thus, they are at the
origin of the name of the central part of the
retina, macula lutea(yellow spot).
 By absorbing blue-light, the macular pigments protect
the underlying photoreceptor cell layer from light
damage, possibly initiated by the formation of reactive
oxygen species. Increasing the intake of lutein or
zeaxanthin may prove to be protective against the
development of age-related macular degeneration.
 Several nutritional investigations have suggested that
lutein supplements may improve visual function and
optical density in aged people.
 Astaxanthin, present in yeast, microalgae, crustaceans and fish, is
a natural nutritional component, used as a food supplement for
human and animal consumption. Its commercial production
comes from both natural and synthetic sources.
 In vitro, astaxanthin is several fold more active as a free radical
antioxidant than b-carotene anda-tocopherol. In animal models,
its modulates immune response, inhibits cancer cell growth, and
reduces bacterial load and gastric inflammation in vitro and
rodent models.
 In humans, dietary astaxanthin decreases a DNA damage
biomarker and acute phase protein, and enhances immune
response.

Astaxanthine
 Ketocarotenoids belong to the xanthophyll group and
are quite unique in nature.
 Among these compounds, echinenone and
canthaxantin are abundant in cyanobacteria are
characteristic of cyanobacteria.
 Violaxanthin is an epoxidized derivative of
antheraxanthin (hydroxylated cryptoxanthin)
and forms with zeaxanthin the xanthophyll cycle that
is said to protect the photosynthetic system of plants
against damage by excess light.
 Two cycloaddition products of trans-violaxanthin
with a-tocopherol have been isolated from seeds
of Pittosporum tobira and their structures elucidated.
 These C69 carotenoids were named
pittosporumxanthins. Their global structure is given
below.
 Further investigations have revealed the existence of six
other forms based on addition of a-tocopherol with
antheraxanthin, neoxanthin or violaxanthin.

Pittosporumxanthin
 Fucoxanthin, as an allenic carotenoid with a 5,6-
monoepoxide group, is one of the most
abundant carotenoid in brown algae and
diatoms.
 This compound contributes more than 10% of
the estimated total production of carotenoids in
nature. Fucoxanthin was first isolated by
Willstätter R et al.

Fucoxanthin
 This carotenoid has shown interesting biological
properties, such as anticarcinogenetic effects, anti-
inflammatory effects and radical scavenging activity.
 Furthermore, it has been shown that fucoxanthin has an
anti-obesity effect in connection with the expression of
the uncoupling protein UCP1 in white adipose tissue.
 Its ability to enhance the docosahexaenoic acid
concentration in the liver of treated obese mice remains
to be examined more thoroughly.
 A great part of the biological properties of fucoxanthin
may be related to its ability to take up peroxynitrite
through the formation of nitrofucoxanthin and the
inhibition of the nitration of tyrosine by peroxynitrite.
 Therefore, fucoxanthin may have the potential to reduce
the risk of cancer induced by reactive nitrogen species.
 Neoxanthin is another common allenic carotenoid,
widely distributed in higher plants and algae, which
was first isolated from the green leaves of barley in
1938 by Strain HH.
 Neoxanthin is thought to be a part of the light
harvesting complexes and as a precursor to the
plant growth hormone abscisic acid.

Neoxanthin
 An unusual carotenoid ester was identified in
fresh mango lipids as violaxanthin dibutyrate.
 Another unusual acetylenic carotenoid was
discovered and identified in a marine sponge.
 That new molecule was shown to be strongly
cytotoxic toward cultured human colon tumor
cells.
 Specificcarotenoids are found in mineral sediments or
crude oils and are used as biomarkers.
 Among them, isorenieratane, found in oils of Devonian
age, is derived from the carotenoid isorenieratene (an
homologue of the previous one but with an
unsaturated isoprenoid chain), which is synthesized by
photosynthetic green sulfur bacteria (Chlorobiaceae).

Isorenieratane
 Another C40 carotenoid, paleorenieratane, also
thought to be derived from the same bacteria has been
identified in Devonian aged sediments and crude oils.
 These green sulfur bacteria are strict anaerobes that
require light and hydrogen sulfide in stratified water
columns to carry out photosynthesis and are thus
markers for these photic zones (euxinic) in
depositional environments.

Paleorenieratane
 C50-carotenoids, including bacterioruberin
which is present in halophilic Archaea,
characterize the colored saltern ponds.

Bacterioruberin
 Although green leaves contain unesterified hydroxy
carotenoids, most carotenoids in ripe fruit areesterified
with fatty acids.
 However, those of a few fruits, particularly those that
remain greenwhen ripe, such as kiwi, undergo limited or
no esterification. Carotenoid mono- and diesters were
identified in mandarin essential oil,
 In Haematococcus pluvialis and in the Antarctic
krill Euphausia superba.
 Carotenoids fatty acid esters were also described in the
carapace of the spiny lobster Panulirus japonicus.
 Astaxanthin, adonixanthin, and pectenolone were
esterified with fatty acids with a large range of chain
length and unsaturation.
 Several esterified seco-carotenoids, the
tobiraxanthins, have been isolated from the
seeds ofPittosporum tobira .
 Two fatty acid molecules (lauric or myristic acid)
acylated the carotenoid part. One of these
compounds is shown below (Tobiraxanthin A1).
 Apocarotenoids are carotenoid derivatives formed by the
removal of fragments of the carbon backbone from
either or both ends of a C40 precursor such as lycopene
or beta,beta-carotene. These modification originate in
the oxidative degradation at the level of the terminal
rings.
 They may be the result of nonspecific mechanisms
(lipoxygenase, photo-oxidation) as well as of specific
mechanisms (dioxygenases).
 They have significant roles as developmental and
environmental response signals. They also make
important contributions to flavor and nutritional quality
of foods (fruits, tea, wine) and tobacco.
 Two well-known apocarotenoids
are bixin and crocetin which have economic
importance as pigments and aroma in foods.
 Bixin (cis- or trans-bixin) is one of several highly colored
molecules extracted from annatto seed coats (Bixa
orellana) and used as a food coloring and cosmetic
compound since pre-Colombian times.
 It was determined that lycopene is the precursor of bixin.
 Crocetin, occurring as various glycosyl esters, is the
coloring principle of saffron, pollen harvested from Crocus
sativus. This apocarotenoid originates in the rupture of
zeaxanthin.
 Two other C26 and C30 apocarotenoids have been
characterized in the seeds of Ditaxis heterantha,
heteranthin and ditaxin.
 The presence of these products explains the use of
the Ditaxis seeds as a natural food flavor and coloring.
 It was shown that several volatile products are
present after enzymatic degradation.
 Among them, the so-called norisoprenoids, the
C13-cleavage products of carotenoids, have
extremely low detection threshold values.

a-Ionone a-Damascone
A peroxidase from edible fungi was shown to be a key
enzyme able to degrade carotenoids into important
flavor compounds (ionone, cyclocitral, terpineol....).
 A review of the oxidative remodeling of plastid
carotenoids initiated by specific dioxygenases has been
released by Camara B et al.
 Furthermore, apocarotenoids act as visual or volatile
signals to attract pollinating agents, and are also key
players in plant defense.
 Studies have shown that the loss of cleavage enzymes
induces the development of axillary branches,
indicating that apocarotenoids convey signals that
regulate plant architecture.
 Itis generally accepted that oxidation of
carotenoids begins with epoxidation and cleavage
to apocarotenals prior a transformation into other
derivatives.
 Several epoxycarotenoids and apocarotenals were
observed in experimental oxidation models but
also some were identified in processed foods.
 The two compounds shown below were detected in
fruit extracts :
 Another apocarotenal, trans-b-apo-8'-carotenal,
is found in spinach and citrus fruits. It has a low
pro-vitamin A activity and is used in
pharmaceuticals and cosmetic products.
 This apocarotenal is also used as an additive
(E160e) legalized by the European commission
for human food.

trans-b-Apo-8'-
carotenal
 Apolycopenals have been reported in laboratory animals consuming high
lycopene diets. Apo-8'- and apo-10'-lycopenal were observed in the
hepatic tissue of rats consuming a high lycopene diet.
 These products are not limited to mammalian systems but were also
identified in extracts of tomato.
 Thus, apo-6'-, apo-8'-, apo-10'-, apo-12'-, and apo-14'-lycopenals
were detected and quantified in tomato (6.5 mg/100 g), apo-12'-
carotenal being the most abundant.
 The presence of multiple apolycopenals in the plasma of humans
consuming tomato juice has been documented.
 This evidence suggests that these products may in fact be absorbed
from the food and not solely a product of metabolism in vivo.
 Abscisic acid is an end product of neoxanthin or violaxanthine
peroxidation and reduction giving an apocarotenal with a short side
chain (5 carbons), followed by a final oxidation into an acid form.

Apo-12'-carotenal
 Trisporoids, derived from b-carotene, regulate the recognition between mating
partners, early sexual morphogenesis and development in zygomycete fungi.
 They are released from the hyphae (sexual cells), exerting their physiological
effects upon compatible mating partners.
 Trisporic acid and some precursors directly influence the transcription of genes
involved in sexual development.
 The connection between b-carotene and trisporic acid was early established
when trisporic acid was established as a substance produced by mated cultures
of strains of Blakeslea trispora andMucor mucedo and as a metabolite of b-
carotene after using 14C labeled molecules.
 As for several other b-carotene derived signal compounds, the first step in
trisporoid synthesis is the oxidative cleavage of b-carotene (b-carotene
oxygenases).

Trisporic acid
 Strigolactones are signaling molecules that play a
double role in the rhizosphere as host detection
signals for arbuscular mycorrhizal fungi and root
parasitic plants.
 In addition to their important role as rhizosphere
signaling compounds, it has recently been
demonstrated that strigolactones also act as new
hormones inhibiting shoot branching in plants and
hence are involved in the regulation of above-
ground plant architecture.
 Since the isolation of strigol as a germination
stimulant for Striga lutea from roots of Gossypium
hirsutum , more than ten strigolactones have been
identified.
 The 5-deoxystrigol is considered as the precursor of
all other strigolactones (Orobanchol, strigol).
 The structural core of the molecules consists of a
tricyclic lactone (ABC part) that connects via an enol
ether bridge to a butyrolactone group (the D-ring).
 All other strigolactones possess one or two methyl
substituents on the A-ring and various combinations
of hydroxyl or acetate substituents around the A-
and B-rings.
 It has been demonstrated that these terpenoids are
derived from the carotenoid pathway.
Carotenoid glycosides
 Carotenoids may be linked to a sugar by a
glycosidic link or an ester link.
 Such compounds are known for plant and
bacteria. As an example, a glucoside of
rhodopsin, found in the photosynthetic part
of Rhodopseudomonas acidophila, is shown
below.
 Salinixanthin is a glycosylated and acylated
carotenoid associated with the protein
xanthorodopsine which was isolated from the
extremely halophilic eubacterium Salinibacter
ruberliving in salt pond in Spain.
 This carotenoid has a keto group in the ring, a
glycoside group and an acyl tail, probably immersed
in the membrane.
 Astaxanthin diglucoside diesters have been determined
in lipid extracts of the snow alga (Chlamydomonas
nivalis).
 The C-3 hydroxyl group of astaxanthin is glucosylated
and the C-6 hydroxyl group of the glucosyl moiety is
esterified with specific fatty acids.
 Among these fatty acids (14 species were detected),
the most abundant were 16:3, 16:4, 18:1, 18:4 and
18:5.
 Carotenoids are said to have antioxidant properties,
as tocopherols, and thus may prevent the oxidation of
the lipid moieties of LDL (low density lipoproteins)
which renders these lipoproteins atherogenic.
 Faraday Michael determined in 1829 that rubber produced by Hevea
brasiliensis was made up solely of carbon and hydrogen and had the
empirical formula C5H8. In 1860, the English chemist Greville Williams C
obtained a liquid with the same formula by distilling rubber, he called it
isoprene.
 In 1879, Bouchardat G obtained isoprene from natural rubber and found that
heating isoprene with HCl produced a rubber-like polymer after distillation.
 He said that this new product had "the elasticity and other properties of
rubber itself".
 This was the first production of artificial rubber. After the early
demonstration that each isoprene unit has one double bond and that rubber
has a high molecular weight, the idea that the rubber molecule consisted of
long chains formed by the regular linking of isoprene units was only slowly
established after the works of Harries CD (between 1902 and 1905) and
mainly of Staudinger H (in 1920) who coined the term "macromolecule".
 It was determined that the hydrocarbon chains were composed of an initial
group w' formed by two or three trans-isomer units, a long chain formed by
a great number of cis-isomer units, and a not yet completely determined
terminal group a .
 The w-terminal linking to proteins was suggested to form
physical cross-links, whereas the a-terminal linking to
phospholipids to form chemical cross-links with long chain
fatty acid ester groups. It was shown that the linked fatty acids
were composed of saturated and unsaturated C10 to C22 fatty
acids, the composition of which was similar to that of mixed
fatty acids.
 It seems that the mechanical properties of natural rubber could
be dependent on the composition of these fatty acids
 If natural rubber is formed by cis-isomer units, the material
known as gutta-percha produced byPalaquium
gutta (Sapotaceae), and balata, formed by Mimusops globosa,
are polyisoprenes having all a trans structure.
 The polymer chains of rubber are very long and have an
average molecular weight more than a million.
 As these long chains are not naturally cross-linked, rubber is
soluble in non-polar solvents and thus may be considered as
lipids.
 Goodyear C found in 1830 the way to harden the
natural rubber in heating the raw product with
elementary sulfur, process which creates chain
cross-links and is now known as vulcanization.
 It must be noticed that while natural rubber is
mainly produced today from Hevea tree, it may be
also obtained from guayule (Parthenium
argentatum), a xerophytic shrub that has been
exploited as commercial sources rubber since the
pre-Columbian times when Indians of Mexico used
it to form balls for their games