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Biol317 Lecture 14
Chapter 13 pp283-297
Web Topic 13.1
Secondary Products and Plant
Defence
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• Nearly all ecosystems contain a wide variety of bacteria, viruses, fungi, nematodes,
mites, insects, mammals, and other herbivorous animals.
• The cuticle (a waxy outer layer) and the periderm (secondary protective tissue) of
plants provide barriers to the entry of bacteria and fungi (and help to prevent water
loss).
• Secondary metabolites not only provide protection for the plant against pathogens
and herbivores, but can have other functions such as structural support.
3 CUTIN, WAXES, AND SUBERIN
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• The principal types of lipid coatings of plant organs are cutin, suberin, and waxes.
• Cutin is found on most shoot organs, whereas suberin is present on underground
parts, woody stems, and healed wounds. Waxes are found with both cutin and
suberin.
5 Cutin, Waxes, and Suberin Are Made Up of Hydrophobic
Compounds
• Cutin is a polymer of long-chain fatty acids attached to each other by ester
linkages, creating a 3D network. Cutin is the main constituent of the cuticle, a
multilayered secreted structure that coats the outer cell walls of the epidermis.
• The cuticle has a thin outer layer of wax, a thick middle layer of cutin embedded in
wax, and a lower layer of cutin and wax mixed with pectin, cellulose, and other
carbohydrates.
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• Waxes are complex mixtures of long-chain acyl lipids that are extremely
hydrophobic. Waxes are synthesized by epidermal cells, and are secreted as droplets
that pass through pores in the cell wall.
• Suberin is a polymer which, like cutin, is formed from hydroxy or epoxy fatty
acids joined by ester linkages, but has dicarboxylic acids, more long-chain
components, and a substantial proportion of phenolic compounds in its structure.
Suberin is associated with the cork cells of the periderm (as well as many other

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14 Cutin, Waxes, and Suberin Help Reduce Transpiration and

Pathogen Invasion
• The cuticle is very effective at limiting water loss but does not block transpiration
completely.
• The thickness of the cuticle varies with environmental conditions, with thicker
cuticles found on plants in arid environments.
• Some fungi penetrate through the cuticle by direct mechanical means, while others
produce cutinase, which breaks down cutin.
15 SECONDARY METABOLITES
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• Secondary metabolites are compounds that have no direct function in growth and
development; i.e., no role in photosynthesis, respiration, solute transport,
translocation, protein synthesis, nutrient assimilation, differentiation, or the
synthesis of carbohydrate, proteins and lipids. They are also called secondary
products, or natural products.
• Individual secondary metabolites have a restricted distribution in the Plant
Kingdom.
17 Secondary Metabolites Defend Plants against Herbivores and
Pathogens
• Many secondary metabolites are suggested to have important ecological functions
in plants.
• These include protection against herbivory and infection by pathogens, as
attractants for pollinators and seed-dispersing animals, and as agents of competition
between plants.
18 Plant Defences Are a Product of Evolution
• Random mutations in primary metabolic pathways led to the production of new
compounds that happened to be toxic or to act as a deterrent to herbivores and
pathogens.
• Providing the new compound was not overly toxic to the plant itself and did not

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 take too much energy to produce, it would give the mutant plant an evolutionary
advantage.
19 Secondary Metabolites Are Divided into Three Major Groups
• These are the terpenes, phenolics, and N-containing compounds.
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21 TERPENES
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• The terpenes (or terpenoids) make up the largest class of secondary products.
• They are generally insoluble in water, and are synthesized from acetyl-CoA or
glycolytic intermediates.
23 Terpenes Are Formed by the Fusion of Five-Carbon Isoprene Units
• Terpenes are built up from 5-C units that have the branched C skeleton of
isopentane. The units are sometimes called isoprene units (because terpenes can
decompose at high temperatures to give isoprene). Thus terpenes may be called
isoprenoids.
• Terpenes are classified according to the number of isoprene units they contain; 2×
isoprene is considered to be “mono”.
24 There Are Two Pathways for Terpene Biosynthesis
• In the mevalonic acid pathway, 3× acetyl-CoA are joined together stepwise to
form mevalonic acid. This is then pyrophosphorylated, decarboxylated, and
dehydrated to give isopentenyl diphosphate (IPP), the activated 5-C building
block of terpenes.
• IPP can also be synthesized via the methylerythritol phosphate (MEP) pathway
in plastids (including chloroplasts).
25 Isopentenyl Diphosphate and Its Isomer Combine to Form Larger
Terpenes
• IPP and its isomer, dimethylallyl diphosphate (DPP), are both activated molecules
that form terpenes. First they reactive together to form geranyl disphosphate (GPP),
the 10-C precursor of nearly all the monoterpenes.
• GPP can then link with 1× IPP to give the 15-C compound farnesyl diphosphate
(FPP), the precursor of nearly all sesquiterpenes.
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• Addition of another 1× IPP gives the 20-C geranylgeranyl diphosphate (GGPP), the
precursor of the diterpenes.
• Finally, FPP and GGPP can dimerize to form the triterpenes (30-C) and the
tetraterpenes (40-C), respectively.

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29 Some Terpenes Have Roles in Growth and Development
• Specific terpenes are not secondary products; i.e., they have a well characterized
function in growth or development.
• Examples include gibberelins (which are diterpenes), sterols (triterpene
derivatives), carotenoids (tetraterpenes), and abscisic acid (a sesquiterpene
produced by degradation of a carotenoid precursor).
30 Terpenes Defend against Herbivores in Many Plants
• Terpenes are toxins and feeding deterrents to many insects and mammals.
• Examples include the pyrethroids (monoterpene esters), which are found in the
leaves and flowers of Chrysanthemum spp., which are powerful insecticides.
• In conifers, monoterpenes toxic to many insects accumulate in resin ducts in
needles, twigs, and the trunk.
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• Essential oils are mixtures of volatile monoterpenes and sesquiterpenes found in
many plants. They confer a characteristic odour to the foliage. Menthol is the main
monoterpene of peppermint oil, while limonene is the corresponding monoterpene
in lemon oil.
• Essential oils act as insect repellents, and are commonly found in glandular hairs
that project outwards from the epidermis.
• In some plants, specific mono- and sesquiterpenes are emitted only after insect
feeding has begun. They repel ovipositing herbivores and attract natural enemies.
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• Phytoecdysones are plant steroids that have the same basic structure as insect
molting hormones. When insects ingest these compounds, molting and other
developmental processes are disrupted, often killing the insect.
• Cardenolides are glycosides that are extremely toxic to higher animals. Those
extracted from species of foxglove (Digitalis) are prescribed for the treatment of
heart disease.
• Saponins are toxic steroid and triterpene glycosides that have detergent properties.
They may interfere with uptake of sterols from the digestive system or disrupt cell
membranes.
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40 PHENOLIC COMPOUNDS
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• Plant phenolics include nearly 10,000 different compounds, all of which contain a
phenol group.
• Many phenolics act as defence compounds against herbivores and pathogens; others
function in mechanical support, in attracting pollinators and animals that disperse
fruits, in absorbing UV radiation, or in reducing the growth of nearby competing
plants.
42 Phenylalanine Is an Intermediate in the Biosynthesis of Most
Plant Phenolics
• There are two basic pathways for the biosynthesis of plant phenolics.
• The shikimic acid pathway (the most important) converts carbohydrates derived
from glycolysis and the pentose phosphate pathway to the aromatic amino acids.
• The herbicide glyphosate kills plants by blocking a step in this pathway.
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• The most abundant secondary phenolic compounds are synthesized via the most
studied enzyme in plant secondary metabolism, phenylalanine ammonia lyase
(PAL). It produces cinnamic acid from Phe via the elimination of NH3. Fungal
invasion triggers the production of PAL, stimulating the synthesis of phenolic
compounds.

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47 Some Simple Phenolics Are Activated by Ultraviolet Light

• Simple phenolic compounds that are widespread in vascular plants include
phenylpropanoids, phenylpropanoid lactones, and benzoic acid derivatives.
• Plants can build on simple phenolic compounds to make more complex products.
• Furanocoumarins, which have an attached furan ring, are not toxic until they are
activated by light.
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50 The Release of Phenolics into the Soil May Limit the Growth of
Other Plants
• The study of the effects of compounds released from leaves, roots, and decaying
litter on neighbouring plants is called allelopathy.
• Simple phenylpropanoids and benzoic acid derivatives are thought to be involved in

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 allelopathy. However, the importance of allelopathy in natural ecosystems is still
controversial for many compounds.
51 Lignin is a Highly Complex Phenolic Macromolecule
• Lignin is the second most abundant organic compound in plants after cellulose.
• Lignin is a highly branched 3D polymer of phenylpropanoid groups, and acts in
both primary and secondary metabolism.
• Coniferyl, coumaryl, and sinapyl alcohols, all of which are sysnthesized from Phe,
are the building blocks of lignin.
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• The proportions of the three alcohols varies among plant species.
• Lignin is found in particular supporting and conducting tissues, including the
tracheids and vessel elements of the xylem. The mechanical strength of lignin
allows upward growth and permits flow through the xylem under negative pressure.
• The toughness of lignin deters feeding by animals, and its chemical durability
makes it relatively indigestible. Lignification can block the growth of pathogens
and is a common response to infection and wounding.
53 There Are Four Major Groups of Flavonoids
• The flavonoids are one of the largest classes of plant phenolics. The basic structure
consists of two aromatic rings connected by a 3-C bridge.
• Both the shikimic acid pathway and malonic acid pathway contribute the basic
flavonoid structure.
• Flavonoids are classified into groups, mainly on the basis of the degree of oxidation
of the 3-C bridge.
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• Flavonoids groups include the anthocyanins, the flavones, the flavonols, and the
isoflavones.
• The majority of flavonoids are glycosides.
• Different types of flavonoids perform distinct functions in the plant, including
pigmentation and defence.
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56 Anthocyanins Are Coloured Flavonoids That Attract Animals

• Animals may carry pollen and seeds for plants in return for being provided with
nectar or fruit. Secondary metabolites are involved in these plant-animal
interactions, helping to attract animals using visual and olfactory cues.
• Anthocyanins give most of the red, pink, purple, and blue colours of plants.
Without their sugars, anthocyanins are known as anthocyanidins.
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• The colour of anthocyanins is influenced by many factors, including the number
and types of chemical groups attached to one of the rings of structure, the presence
of aromatic rings esterified to the main skeleton, and the pH of the vacuole in which

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60 Flavonoids May Protect against Damage by Ultraviolet Light

• Flavones and flavonols are two major groups of flavonoids. They absorb light at
shorter wavelengths than do anthocyanins, making them invisible to humans.
However, many insects can see into the UV and can thus visually respond to these
compounds.
• Flavonols in a flower often form nectar guides, which are symmetric patterns of
stripes, spots, or concentric circles.
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• Flavones and flavonols are found not only in flowers but in leaves of all plants.
They protect cells from excessive UV-B radiation (280-320 nm) by accumulating in
the epidermal layers of leaves and stems, and absorbing UV light (while allowing
visible light to pass through).
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64 Isoflavonoids Have Antimicrobial Activity

• Isoflavonoids (isoflavones) are a group of flavonoids in which the position of one
aromatic ring is shifted.
• They are found mostly in legumes and have several different activities, including
insecticidal and anti-oestrogenic effects.
• Isoflavonoids can act as phytoalexins, which are antimicrobial compounds
synthesized to limit the spread of the invading pathogen.
65 Tannins Deter Feeding by Herbivores
• Tannins are divided into two types:
Condensed tannins are formed by the polymerization of flavonoid units, and are
commonly found in woody plants.
Hydrolyzable tannins are heterologous polymers containing phenolic acids and
simple sugars. They are smaller than condensed tannins and are more easily
hydrolyzed.
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• Tannins reduce the growth and survival or many herbivores when eaten. They act as
feeding repellents to a wide variety of animals including mammals. Very high
levels of tannins are found in unripe fruits.
• The tannins in red wine may reduce the risk of heart disease associated with
moderate consumption. However, generally tannins are toxic, as they bind proteins
nonspecifically.
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