SHET 2301

Metabolite and Secondary Metabolism

Lecture 1

House rules
To maximize our learning, lets agree on some rules:
Please be on time 12pm
Please turn off your handphone or switch your
handphone to silent mode

Course outcomes
To identify main secondary metabolites of commercial
importance
To select secondary metabolites in nature for industry
To assess the importance of metabolic pathways in
production of secondary metabolites

Reference materials

Harborne JB. (1973). Phytochemical Methods A Guide to Modern

Techniques of Plant Analysis. Chapman and Hall, London.

Geissman TA and Crout DHG. (1969). Organic Chemistry of Secondary

Plant Metabolism. Reeman, Cooper & Company, New York.

Torsell Kurt BG. (1983). Natural Product Chemistry A Mechanistic and

Biosynthetic Approach to Secondary Metabolism. John Wiley & Sons.

Nicolaou KC and Montagnon T. (2008). Molecules That Changed The World.

Wiley-VCH.

http://spectrum.um.edu.my/

Outline

Primary and secondary metabolism - definitions

Function of secondary metabolites

Classification of secondary metabolites

Primary metabolism
Primary metabolism comprises the chemical processes
that every plant must carry out every day in order to
survive and reproduce its line

Photosynthesis

Synthesis of coenzymes

Glycolysis

Synthesis of structural materials

Citric Acid Cycle

Duplication of genetic material

Synthesis of amino acids

Reproduction of cells (growth)

Transamination

Absorption of nutrients

Synthesis of proteins and enzymes

Photosynthesis is the primary synthetic process of

nature.

The green plants utilize the energy from the sun for the
production of organic compounds from CO2

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Primary metabolites

Primary metabolites are compounds that are commonly

produced by all plants and that are directly used in plant
growth and development

The main primary metabolites are carbohydrates,

proteins, nucleic acids, and lipids

Primary metabolites are precursors of secondary

metabolites

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Plant metabolism

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Secondary metabolites

Do not have apparent functions involved in plant growth and

development
non-nutritional chemicals

Produced in different plant families, in specific groups of plant

families or in specific tissues, cells or development stages
throughout plant development

Most plants have not been examined for secondary

compounds and new compounds are discovered almost daily

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Secondary metabolites has more complex structures than

primary metabolites

Natural products : recognized by chemists as secondary

metabolites

Example: biphenols, alkaloids, terpenoids and flavonoids

No sharp division line between primary and secondary

metabolites.

Found in plants, microbes, mushrooms, fungi, seaweeds.

Rarely in animals

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Products of secondary plant metabolism

Chlorophyll + CO2 + light

photosynthesis
Carbohydrates

Pentose cycle

glycolysis

Phosphoenolpyruvic acid

Shikimic acid

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Pyruvic acid

Products of secondary metabolism

Shikimic acid

Pyruvic acid

Alkaloids

Aromatic amino acids

Cinnamic acids

Amino acids

Phenylpropanoid compounds

Acetyl coenzyme A
Krebs cycle
acids

Malonyl coenzyme A

Fatty acids

Flavonoids
compounds
Polyketides

Polyacetylenes
Phenolic
compounds

Mevalonic acid
Terpenoids Compounds
Steroids
Carotenoids

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Some naturally occurring compounds

discovered in the early 1800s
Year

Compound

1817

Morphine

1817

Narcotine

1820

Quinine

1821

Caffeine

1834

Creatine

1834

Cinamic acid

1859

Cocaine

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Functions of secondary metabolites

Important to mankind:

Antibiotics kill microbes that cause infections

Defence purposes

Example: Memosine from Mimosa pudica can cause animals

that feed on plant to loose furs

Chemopreventive properties

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Example: Penicillin from Penicillium cephalosporin

Example: Curcumin (from C. longa-tumeric) and many other

metabolites

Growth hormone

Example: gibberellin, indolylacetic acid (heteroauxin) controls

formation of new plant cells

Hormones for the repair of wounded tissues

As attractants for insect and birds

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Example: traumatic acid

Example: colours and odour from flowers to assist in

pollination, dispersion of seeds, anthocyanins (give colour to
plants), flavonoids , carotenoids (red colour)

Functions of secondary metabolites

As repellents
Plants produce unpleasant odours and taste directed to humans,
animals and insects - for defence and alarm

Fungicide / antibiotics
to protect plants from fungi / bacteria
phytoalexin is a compound produced by plants when attacked by
fungi

Poisons
to humans, insects
saponins are poisonous to insects
cyanogenic alkaloid glycosides
bitter taste as insect detractors

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Classification of secondary metabolites

There are many system of classifications:

Chemotaxonomic

Biogenetic

Based on physiological activities

Based on chemical structures

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Chemotaxonomic classification
Chemotaxonomy

A study to show relationship between natural products and

taxa of plants responsible for the production of natural
products (secondary metabolites)

The chemicals (metabolites) can be used to identify a

particular species of plants

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However, many secondary metabolites are very widely

distributed that they cannot be used as taxonomic
identification
Example: sitosterol, stigmasterol, gallic acid and catechol
are commonly found in many plants
Some groups of compounds - alkaloids are typically found in
certain species of plants only. Thus, useful for
chemotaxonomic identification

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Biogenetic classification

Biogenesis / biosynthesis primary and secondary metabolites

Theory of biosynthesis of phenols (Robinson, 1955)
Isoprene Rule (Ruzicka, 1938)
Terpenoids formed through head-to-tail joining of 5-carbons units
called isoprene.
1 unit isoprene
C5 Isoprenes
2 units isoprene
C10 Monoterpenes
3 units
C15 Sesquiterpenes
4 units
C20 Diterpenes
6 units
C30 Triterpenes
8 units
C40 Tetraterpenes
> C40
Polyisoprenes

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Classification based on physiological

activities

Vitamins

Hormones

Antibiotics

Mikotoxines

Each class of compounds has specified activities. However the

compounds within each class are not structurally related.
Antibiotics

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Classification based on chemical

structures

Before classification on biosynthesis was known, compounds from

natural sources were classified according to chemical structures.
Aromatic compounds
Those possessing aromatic rings
Example: phenolics, quinones, flavonoids

Heterocyclic compounds
Example: Nucleic acids, alkaloids, coumarins, flavonoids

Aliphatic compounds
Example: carbohydrates, lipids, terpenes, amino acids

Not so good! Overlap in classifications.

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Example: Indole alkaloids: aromatic, heterocyclic

Classification of secondary metabolites

Currently most natural products can be classified into 3 major

groups :

Phenolic compounds
Flavonoids, anthocyanin, salicylic acid, lignin

Terpenes
Limonoids, saponins, pinene

Nitrogen containing secondary products

Alkaloids, nicotine, morphine, cocaine, caffeine, glucosinolates

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Phenolics

Compounds that contain a fully unsaturated six carbon ring

linked to an oxygen are called phenolics

Salicylic acid (basic part of aspirin) is a simple phenol.

Myristicin is a more complex phenol that provides the flavor of

nutmeg.

Flavonoids are complex phenolics. They are often sold in

health food stores as supplements to vitamin C. The most
commonly available flavonoid is rutin from buckwheat

Anthocyanins are a type of flavonoid that give flowers red and

blue pigments.

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Some phenolics form polymers.

Tannins are astringent to the taste. They give dryness

(astringency) to dry wines. They can also be used to tan
leather. They often give water a tea-colored look. Tannins are
common in pines and oaks.

Lignin is a major structural component of wood. The exact

structure of lignin is complex and not known.

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Terpenoids

Terpenoids are dimers and polymers of 5 carbon precursors called

isoprene units (C5 H8).

Terpenoids often evaporate from plants and contribute to the haze

we see on hot sunny days. They are expensive to make; they often
take 2% of the carbon fixed in photosynthesis; carbon that could
otherwise be used for sugars.

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Alkaloids

Alkaloids generally include alkaline substances that have nitrogen as part of

a ring structure.

More than 6500 alkaloids are known and are the largest class of secondary
compounds.

They are very common in certain plant families, especially:

peas Fabaceae

sunflower Asteraceae

poppy Papaveraceae

tomato Solanaceae

dogbanes Apocynaceae

milkweeds - Asclepiadaceae

citrus Rutaceae

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