Secondary

Metabolites

Metabolism is a very complicated set of topics

Scope
Synthesis, physiological roles, ecological roles of plant secondary metabolites

Four classes (based on structural and biosynthetic pathway components:
Terpenes
Phenolic compounds
Alkaloids
Glycosides

Secondary metabolites
The organic molecules that are essential to cell function (respiration,
photosynhtesis, etc.) are called primary metabolites
Plants divert a significant fraction of assimilated carbon and energy to
secondary metabolites that are not essential to cellular function, but are
beneficial
Also called natural products, are derived from primary metabolites but are
typically found at much lower concentrations
These compounds often have medicinal or economic value
Natural products is now an emerging research worldwide

Some primary metabolites are synthesized through secondary

metabolism

General uses of secondary metabolites
Reduce the impact of insect and animal predation
Provide protective functions
Serve as folk remedies, soaps, essences, medicinal products, dyestuffs, feed
stocks for chemical industries (e.g., gums, resins, rubber)
Some substances used to flavor food and drinks

Major classes of Secondary metabolites
Terpenes
Synthesized in the Mevalonic Acid Pathway
Phenolic compounds
Synthesized in the Shikimic Acid Pathway

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 Alkaloids
Nitrogen containing secondary metabolites
Glycosides
With sugar side chains

Phenols; largest group derived from alphaketoglutarate forming amino acids
Flavonoids (pigments; anthocyanins)
Derived from acetyl-CoA where aCoA is condensed into malonyl
CoA
Tannins (hydrolyzable condensed)
Lignin (synthesized from the pentose phosphate pathway
Alkaloids from amino acid also

Terpenes
Synthesized from isoprene subunites
Functionally and chemically diverse lipophilic substabces derived from a simple
Biosynthetic relationship between primary and secondary metabolites 5-C unit, the 2-methyl-1,3-butadiene
Isoprenoid compounds
However, the actual building blocks are not isoprene itself, but 2
phosphorylated derivatives
Isopentyl pyrophosphate or active isoprene
Dimethylallyl pyrophosphate (isomer of active isoprene
Mevalonic acid pathway: common biosynthetic pathway shared by all terpenes
and its derivatives

Mevalonic Acid Pathway

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Naturally occuring cytokinins derived from this pathway

Geranyl pyrophosphate
monoterpenes
Farnesyl pyrophosphate
Sesquiterpenes (Abscisic Acid)
Trierpenes (Steroids
Geranylgeranyl pyrophosphate
Diterpenes (gibberellins; chlorophyll phytol tail)
Tetraterpenes (carotenoids)

Examples of terpenes include
Gibberellins
Carotenoid pigments
Sterols (cholesterol)
Sterol derivatives (cardiac glycoside)
Latex
Essential oils

Classes of Terpenes

Essential oils

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 10-c terpenoids that create the characteristic odor of mint and many herbs
These are volatile compounds often stored at or on the leaf surface in glands or
cells
Ironically, these compounds also contribute to some aspect of air pollution

Monoterpenes

Memorize the names of these compounds

Meron din yung botulin, which was first isolated from Clostridium botuline
Epidermal glandular hair on leaf surface with secretory cells producing essential oils
Steroids and Sterols
Cyclic terpenoids with < 30 carbons
Primary function of plant sterols is to increase viscosity and enhance the
stability of plant membranes
Sterols, such as phytoecdysones defend against insect herbivores by emulating
plant molting hormones

Phenylpropanoids
Derivatives of the simple hydroxylated aromatic ring, phenol
Phenolics or polyphenos
Uses:
Defense against herbivory
Structural components (lignin)
Simply metabolic end-products with no-known function
Examples
Lignin and tannins
Flavonoid pigments
These are derivatives of the simple hydroxylated aromatic ring, phenol
Building blocks
Phenylalanine and tyrosine
Phenylalanine --> cinnamic acid ---> p-coumaric acid ---> caffeic acid--
>lignin
tyrosine---> p-coumaric acid ---> caffeic acid-->lignin
Coumarins
Basic structures
most abundant sterols in higher plants are stigmasterol and sitosterol (Figure Lignin is a large, irregular polymer of monolignols
27.6), which often make up more than 70 percent of the total sterols Monolignols
More than 150 known to occur in nature Difference of coniferyl alcohol and sinapyl alcohol
Flavonoid
Polyterpenes Pollinator attraction (anthocyanin pigments)
More than 40 carbons Phytoalexins
Ex. Carotenoids Synthesis:
Larger polyterpenes are rubber and gutta Derived from malonyl-CoA from acetyl CoA
15000 isopentyl subunits, differing only in double bond config (cis=rubber; Chalcone synthase
trans=gutta) Catalyzes the first committed step in the biosynthesis of
Rubber occurs in small particles in the latex from plants flavonoids such as naringenin
Latex is produced in the phloem and is stored in laticifers Naringenin is a precursor for flavonoids such as kaempferol
Gutta is obtained from the desert shrub guayule (Partenium argentatum) and quercitin
Precursor of tannins
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 Ring structure and stilbenes are both synthesized by sequential
condensations of 3 molecules of malonyl-coenzyme A, with either
cinnamoyl-coenzyme A or p-coumaroyl-coenzyme A
Tannins
2 types:
Condensed tannins
Polymers of flavonoid units linked by strong carbon bonds
Hydrolyzable tannins
Can be oxidized by strong acids
Gallic acid can capture free radicals

Shikimic acid Pathway
Synthesis of phenylpropanoids
Aromatic amino acids (phenylalanine, tryptophan, and tyrosine) are synthesized
by the Shikimic Acid Pathway
Synthesis begins with erythrose-4-phosphate and phosphoenolpyruvate (from
glycolysis) which will form shikimate (shikimic acid)
Shikimate converted to chorismate
Pathway branches after chorismate so that one branch leads to phenylalanine
and other amino acids

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Plant Growth and Development

(no synthetic pathways of hormones)
Major mechanisms nalang
Read on phytohormones
Internal and external signals
Basic concept on growth and development

Focus on the control; stimuli/signals (phytohormones and major environmental
factors)

Growth morphogenesis and Differentiation: formation of the plant body
Development
o Refers to the sum of all the changes that an organism goes through its
life cycle
The 3 development processes: growth, morphogenesis, and cellular
differentiation act in concert to transform the fertilized egg into a plant
Growth
o A quantitiative term related to changes in size and mess
Differentiation
o Qualitative term
Pathway starts with Erythrose-4-phosphate and Phosphoenolpyruvate o Refers to differences other than size among tissues, cells, and organs;

Is it a primary or secondary pathway? Why? process involved in assuming different anatomical characteristics and
Answer for exam functions
Morphogenesis
Alkaloids o Refers to development of body form and organization
Are secondary metabolites that
Are soluble in water Plant growth: cell division and expansion
Contain nitrogen Cell division in meristems increases the potential for growth by increasing cell
Have high biological activity number
Alkaloids are generally heterocyclic, but some ar allipathic Cell expansion accounts for the actual increase in plant size
Diversity due to amino acid diversity
The plane and symmetry of cell division
Glycosides The plane (direction) and symmetry of cell division are immensely important in
Cardiac determining plant form
Cyanogenic If the planes of division are parrallel to the plane of the fisrt division, a single file
Glucosinolates of cells is produced
Saponins



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The Preprophase Band
Plane in which a cell divides is determined during late interphase
Microtubules become concentrated into a ring called the preprophase band Orientation of cell Expansion
Fragmoplast pag di pa nakadugtong; coalese to form the cell plate Usually oriented along the plant's main axis

Microtubules and plant growth
Studies of fass mutants of Arabidopsis have confirmed the importance of
cytoplasmic cell division and expansion
Fasss gene: involved in normal microtubule organization
The fass mutant has a s

Growing plant cells expand mainly through water uptake and cell wall loosening

Model for stress relaxation in the cell wall during growth

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 Morphological differences
Physiological properties

Axial polarity

In the gnom mutant of arabidopsis, the establisment of axial polarity is

defective
Normal 1st division is asymmetrical-- initiating polarization into root and shoot
Gnom mutant: abnormal cell division; symmetrical; ball-shaped plant with no
roots and leaves
Defect in this mutant has been traced to the inability to transport the hormone
auxin in a polar manner

Control Growth and Development
Intrinsic controls
o Expressed at both the intracellular and extracellular levels
o Intracellular controls: genetic, requiring a programmed sequence of gene
expression
o Extracellular controls: hormonal, chemical messengers that allow cells to
communicate with one another
Morphogenesis and pattern formation Extrinsic controls: environmental cues such as light, temperature, and gravity
Pattern formation is the development of specific structures in specific locations
It is determined by positional information in the form of signals (genes or ABC Hypothesis
hormones), indicating to each cell its location
Polarity
o One type of positional information
o Condition of having structural differences at opposite ends of an
organisms

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Functions overlap

Signal transduction pathways link signal reception to response
Plants have cellular receptors that detect changes (signals) in their environment
For a stimulus to elicit a response, certain cells must have and appropriate
receptor
Controls = signals/stimuli

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Reception, transduction, and response
Internal and external signals are detected by receptors
Auxin
Plant hormones help coordinate growth, development, and responses to stimuli The term auxin refers to any chemical that promotes elongation of coleotiles
Idoleaceticacid (IAA) is a common auxin in plants; the term auxin specifically
Plant growth regulators refers to IAA in this lecture
Organic compounds, either natural or synthetic, that modify or control one or The auxin is produced in shoot tips and is transported down the stem
more specific physiological processes within a plant Auxin is
The term can be used synonymously with plant hormones (phytohormones) but
adhering to the criterion that phytohormones are active at very low Role of auxin in cell elongation
concentrations According to the acid growth hypothesis, auxin stimulates proton pumps in the
plasma membrane
Overview of Plant Hormones The H+ pumps lower the pH in the cell wall, activating expansins, enzymes that
(campbell) loosen the wall's fabric
Cellulose loosening and turgor cause the cell to expand and elongate
Reading assignement: the discovery of plant hormones
Charles darwin and his son francis
Boysen-jensen
Frits Went

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 Higher auxin levels --> root formation

Control of Apical Dominance
Cytokinins, auxins, and other factors (e.g. strigolactones) interact in the control
of apical dominance, a terminal bud's ability to suppress development of
axillary buds
If the terminal bud is removed, plants become bushier
Cytokinins-- promote lateral bud growth
Auxin-- enhances apical dominance
Strigolactone synergistic with auxin

Expansins is a mixture of enzymes; karamihan hydrolases that breakdown
crosslinkages in polysaccharide
Expansins favor acidic pH

Lateral and Adventitious Root formation
Auxin is involved in lateral and adventitious root formation and root branching
Treating detached leaves or stems with auxin causes adventitious roots to form
near the cut surface
An arabidopsis mutant that exhibits extreme proliferation of lateral roots has
auxin 17-fold higher in concentration than normal

Other effects of Auxin
Auxin affects secondary growth by inducing cell division in the vascular
cambium and influencing differentiation of secondary xylem
It promotes growth of fruits in plants, by synthesizing auxin in developing seeds

Auxins as Herbicides
An overdose of auxins can kill eudicots, a clade (group of species) consisting of
the vast majority of flowering plants that


Cytokinins Anti-aging effects
Named because they stimulate cytokinesis (cell division) Cytokinins retard the aging of some plant organs by inhibiting protein
Cytokinins act in concert with auxins: breakdown, stimulating RNA and protein synthesis, and mobilizing nutrients
o Stimulate cell division (auxin only cell growth w/o cell division) from surrounding tissues
o Influence the pathway of cell differentiation in tissue culture (auxin:
Example: delay of leaf senescence
cytokinin ratio)
Approproate hormone levels --> callus formation (undifferentiated Gibberellins
cells) Stem elongation
Higher cytokinnin levels --> development of shoot buds
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 Fruit growth
Seed germination

Stem Elongation
Gibberellins stimulate growth of leaves and stems
In stems, they stimulate cell elongation and cell division

Internode length increases

Germination
Fruit growth
After water is imbibed, release of gibberellins from the embryo signal seeds to
In many plants, both auxins and gibberellins must be present for fruit to set
germinate
Gibberellins are used in spraying of thompson seedless grapes
1. Embryo releases GA which sends the signal to the alleuron

Abscisic Acid
Seed dormancy
Drought tolerance

Seed Dormancy
Seed dormancy ensures that the seed will germinate only in optimal conditions
Precocious germination was observed in maize mutants that lack a functional
transcription factor required for ABA action

Mobilization of Nutrients by GA during Seed Germination
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Jasmonates
Small group of related molecules derived from the fatty acid linolenic acid; first
isolated from jasmine flowers

Strigolactones
Carotenoid-derived hormones produced in roots in response to low phosphate
conditions or high auxin flow from the shoot

Ethylene
Drought
Flooding
Mechanical pressure (triple growth response)
Injury
Infection

7:15 tayo next meeting

Ethylene
Plants produce ethylene in response to stresses such as:
o Drought
o Flooding
o Mechanical pressure
o Injury
o Infection
Mainly on mechanical stress
Triple response to mechanical stress
o Ethylene induces the triple response, which allows a growing shoot of a
Drought Tolerance seedling to avoid obstacles againsts its growth
ABA is the primary internal signal that enable plants to withstand drought o This triple response consists of:
o At the start of wilting, ABA accumulates in the leaves and causes rapid Slowing of stem elongation
closure of stomata, reducing transpiration and preventing further water Thickening of stem
loss Horizontal growth
"water-reducing hormone"
Role of ABA in guard cell movement:
o By affecting second messengers such as Ca, ABA causes K channels in the
plasma membrane of guard cells to open, leading to loss of K+ from the
cells
o This results to osmotic loss of water reducing guard cell turgor which
leads to closing of stomatal pores

Brassinosteroids
Similar to cholesterol and the sex hormones of animals
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Ethylene insensitive mutants fail to undergo triple response after

exposure to ethylene
EIN: ethylene insensitive mutant Apoptosis: Programmed Cell Death during Senescence
CTR: constitutive triple response o Antagonistic to cytokinin
o A burst of ethylene is associated with apoptosis, the programmed
destruction of cells, organs, or whole plants
o Apoptosis requires new gene expression involving formation of enzymes
for the hydrolysis of many chemical components
o Ethylene is almost always associated with apoptosis of cellls during
senesence
Leaf abscission
o A change in the balance of auxin and ethylene controls leaf abscission,
the process that occurs when a leaf falls
o An aging leaf producess less and less auxin
o The abscission layer is a vertical band of parenchyma cells (most
mechanically active cells) at the base of the petiole
o As the influence of ethylene on this tissue layer prevails, the cells
produce enzymes that digest the cellulose and other components of cell
walls

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o Cork cells protect leaf prior to abscission

Fruit Ripening
o A burst of ethylene production in a fruit triggers the ripening process
o The phototrophic bending toward light is caused by a photoreceptor that
o A rare example of positive feedback in physiology: Ethylene triggers is sensitive to blue and violet light, particularly blue light
ripening, and ripening then triggers even more ethylene production. The 2 major classes of light receptors:
o Blue-light photoreceptors (Cryptochromes)
signal to ripen spreads from fruit to fruit, because ethylene is a gas
o One bad apple does spoil the lot o Phytochromes
o CO2 inhibits ethylene synthesis; circulating air prevents ethylene from Blue-light photoreceptors
o Cryptochromes
accumulating
Control
Responses to Light and the Phytochrome system Hypocotyl elongation
Stomatal opening
Responses to light are critical for plant success
o Light cues many key events Chloroplast movement
o Effect of light is called photomorphogenesis Phototropism
Plants direct not only presence of light but also direction, intensity, and Phototropin is the protein kinase that mediates these responses
wavelength Phytochromes as photoreceptors
o Phytochromes regulate many of a plant's responses to light throughout
A graph called an action spectrum depicts relative response of a process to
its life
different wavelengths of light
o Consists of 2 identical proteins joined to form 1 molecule
Action spectra are useful in studying any process that depends on light
Role of phytochrom in the De-etiolation (Greening) Response

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o Reception
o Transduction
Second messengers transfer and amplify signals from receptors to
proteins that cause responses
Two types of second messengers play an important role in de-
etiolation: Ca2+ ions and cyclic GMP
o Response
o Transcriptional regulation
o Post-translational modification of preexisting proteins
De etolation Greening Response
o De-etiolation activates enyzmes that:
Function in photosynthesis directly
Supply the chemical precursors for chlorophyll production The photoreceptor responsible for the opposing effects of red and far red light
Affect the levels of plant hormones that regulate growth is phytochrome
Phytochromes and seed germination Phytochromes exists in 2 photoreversible states
o Effects of red and far red light on germination of lettuce seed o With conversion of Pr to Pf triggering many develupmental processes

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Biological clocks and circadian rhythm

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