Ecological

Biochemistry
CH: 4
2022-2023
▪ Introduction

Plants contain a vast array of compounds referred to as

secondary metabolites that play no role in primary catabolic or
biosynthetic pathways. Many of these metabolites influence
important ecological interactions (e.g., deterring herbivores,
protection against pathogens, allelopathy, symbiotic associations,
seed germination of parasites, or interactions with pollinators).
Others provide protection against ultraviolet radiation or high
temperatures. Some of these roles have already been discussed.
This chapter discusses the role of secondary compounds in
allelopathic and plant—herbivore interactions.
Allelopathy (Interference Competition)
❑ Some plants harm the growth or development of surrounding
plants by the release of chemical compounds: allelopathic
compounds or allelochemicals.
❑ These allelopathic effects are invariably negative, and the
compounds may come from living roots or leaves or from
decomposing plant remains .
❑ Other released compounds may have positive effects, such as
the carboxylates that solubilize phosphate in the rhizosphere
or chelate Al metals and avoid Al toxicity.
❑ These positive effects are not referred to as interference
competition or allelopathy.
❑ [the word allelopathy is derived from two Greek words: allelon (of
each other) and pathos (to suffer)]
❑ The chemicals involved in positive interactions, however, may still
be referred to as allelochemicals.
❑ Some species, e.g., Lupinus sericeus (silky lupine) and Gaillardia
grandiflora (blanketflower) are resistant to the allelochemical [(+)-
catechin] released by Centaurea maculosa, because they release
increased amounts of oxalate upon exposure to catechin. Oxalate blocks
generation of reactive oxygen species and reduces oxidative damage
generated in response to catechin.
❑ Genotypes of one species, e.g., Triticum aestivum (wheat) differ
substantially in the rate at which they release allelochemical phenolics . This
characteristic has potential in integrated weed management, because the
wheat genotypes that release most phenolics tend to have the greatest
capacity to suppress the weedy grass Lolium rigidum (annual ryegrass) .
❑ Benzoxazinoid (cyclic hydroxamic acids) are common allelochemicals in root
exudates from Triticum aestivum (wheat), Zea mays (corn), and Secale
cereale (rye).
❑ In soil, the exudates may be converted into other benzoxazinoids, many with
a similar phytotoxic effect .
❑ Allelopathic compounds may have originally evolved as compounds that
deter pathogens or herbivores and subsequently become involved in
interactions between higher plants. Secretory glands were well developed in
the early gymnosperms and angiosperms of the Paleozoic before there were
terrestrial herbivores, but after the evolution of terrestrial fungi which
suggests that early defense systems may have been directed at pathogen The
mode of action of most allelopathic compounds is unknown.
❑ Many phenolic compounds inhibit seed germination of
grasses and herbs, and they may inhibit ion uptake or
respiration. Volatile terpenoids can inhibit cell division.
Potentially allelopathic compounds can be detoxified by
some species through mechanisms .
❑ The allelopathic effects of Juglans nigra (black walnut)
illustrate the multiplicity of ecological effects. In a zone
up to 27 m from the tree trunk, many plants [e.g.,
Solanum lycopersicum (tomato), Medicago sativa
(alfalfa)] die.
❑ The toxic effects are due to the leaching from the leaves,
stems, branches, and roots of a bound phenolic
compound, which undergoes hydrolysis and oxidation in
the soil.
❑ The bound compound, which is nontoxic itself, is the 4- glucoside of
1,4,5-trihydroxy-naphthalene. It is converted to the toxic
compound juglone (5-hydroxynaphtoquinone).
❑ Some species are resistant to juglone [e.g., Poa pratensis (Kentucky
bluegrass)], probably because they detoxify this allelochemical .
Juglone severely inhibits the relative growth rate, photosynthesis,
stomatal conductance, and respiratation of Zea mays (corn) and
Glycine max (soybean), when applied at a concentration of 10 mM
or more. This concentration can be found in soil under black walnut
when it is used in alley cropping .
❑ Sorghum species have a reputation for suppressing
weed growth, due to the exudation of
allelochemicals. One of these is a dihydroxyquinone
(sorgoleone), which inhibits mitochondrial
respiration and electron transport in photosystem II
.
❑ very few weeds occur under trees of Leucaena
leucocephala (white leadtree) plantations in
Taiwan. This has been ascribed to the presence of
high concentrations of mimosine (a toxic
nonprotein amino acid) as well as a range of
phenolic compounds, which originate from the tree
leaves and inhibit germination and growth of many
forest species .
❑ Allelopathic interactions also appear to play a major
role in desert plants [e.g., between Encelia farinosa
(brittlebush) and its surrounding plants in the Mojave
desert in California, USA]. In many of these plants, a
simple benzene derivative is produced, primarily in the
leaves. It is released when the leaves fall to the ground
and decompose.
❑ An example of growth inhibition by a toxin produced in
roots, rather than leaves, is that of the rubber plant
guayule (Parthenium argentatum). The aromatic
compound , remarkably, causes inhibition of plants of
the same species (autotoxicity). Similar examples of
autotoxicity have been found for cultivars of Triticum
aestivum (wheat) in bioassays under laboratory
conditions .
❑In several cucurbit crops [e.g., Citrullus lanatus (watermelon), Cucumis
melo (melon), and Cucumis sativus (cucumber)], autotoxicity contributes
to ‘‘soil sickness’’; that is, a reduction in yield when crops are grown on the
same plot without rotation. Cinnamic acid is one of the autotoxic
compounds in cucumber; it induces formation of reactive oxygen species
(ROS)
❑ Allelopathic and autotoxic effects probably play a role
in many environments; however, it is hard to estimate
their ecological significance. Some of the released
compounds are probably decomposed rather rapidly
by microorganisms, thus diminishing their potential
effects. Other allelopathic compounds decompose
rather slowly, including a group of phenolic
compounds mostly referred to as tannins.
❑Allelochemicals may also affect soil microorganisms
and thus indirectly affect surrounding plants.
❑For example, monoterpenes from Picea abies
(Norway spruce) inhibit nitrification, either directly or
indirectly due to immobilization of mineral nitrogen.
❑ Exudates released by some plants,
e.g., Eragrostis curvula (weeping
lovegrass) are antagonistic against
plant—parasitic nematodes . These
nematicidal compounds such as
glucosinolates.
Detoxification of Xenobiotics by Plants: Phytoremediation
✓ Plants, like any other organisms in the environment, are continually exposed
to potentially toxic chemicals: xenobiotics.
✓ These xenobiotics may be natural secondary plant chemicals, which we
discussed in this chapter, industrial pollutants, or agrochemicals.
✓ Many xenobiotics are lipophilic; they are therefore readily absorbed and
accumulate to toxic levels within the plant, unless effective means of
detoxification are present.
✓ if plants have pathways to produce and cope with a vast array of natural
secondary chemicals, can they also be put to use to clean up environmental
pollutants .
✓ In this section we discuss the capacity of some plants to detoxify organic
pollutants .The cellular detoxification systems of plants dispose of the
xenobiotics by two sequential processes:
1. Chemical modification
2. Compartmentation
✓ The reactions responsible for chemical modification of lipophilic xenobiotics
involve hydrolysis or oxidation that makes the chemicals more hydrophilic
and creates reactive sites by the addition or exposure of functional groups
(e.g., hydroxyl or carboxyl groups)
(step I); the modified chemicals may still be toxic.
(step II); The next step is the conjugation of the modified xenobiotic.
(step III); followed by export from the cytosol.

✓ Hydrolysis of the xenobiotics in phase I is catalyzed by various esterases

and amidases, but the major reactions are oxidations catalyzed by the
cytochrome P-450 system, which involves mono-oxygenases that insert one
atom of oxygen into inert hydrophobic molecules to make them more
reactive and water-soluble.
✓ The rates of chemical transformation and the types of metabolites that are
formed depend on plant geno type and accounts for variation in herbicide
resistance and tolerance to pollutants.
✓ In phase II, the (modified) xenobiotic is deactivated by covalent linkage to
endogenous hydrophilic molecules (e.g., glucose, malonate, or glutathione)
which produces a water-soluble nontoxic conjugate.
✓ Export of the conjugates from the cytosol to the vacuole or apoplast (phase
III) occurs by membrane-located transport proteins. This detoxification
pathway shares many features with the pathway used by plants for the
vacuolar deposition of secondary metabolites (e.g., anthocyanins)
✓ One important detoxification mechanism is chemical modification of the
xenobiotic by covalent linkage to tripeptides like glutathione.
✓ Conjugation with xenobiotics may take place spontaneously or may
require catalysis by glutathione-S-transferase.
✓ Glutathione is an important plant metabolite that acts both as a reducing
agent that protects the cell against oxidative stress and guards against
chemical toxicity via the modification reactions of phase II.
✓ Glutathione conjugates that are deposited in the vacuole can undergo
further metabolism. For example, the glycine residue of the glutathione
moiety may be removed enzymatically which is sometimes followed by
enzymatic removal of the glutamic acid residue .The glutathione-
mediated and related detoxification systems probably evolved for the
metabolism and compartmentation of natural substrates.
✓ For example, a glutathione-S-transferase is required for the synthesis of
anthocyanins; it produces a glutathione conjugate that can be
transported to the vacuole. Cytochrome P-450 is, similarly, involved in
anthocyanin biosynthesis. Therefore, the selective mechanisms that led
to the catalytic proteins of the pathway that has an apparent specificity
for industrial chemicals are probably associated with the metabolism of
natural secondary plant products,including allelochemicals and pigments .
✓ Higher plants, unlike microorganisms and animals, are unable to
catabolize xenobiotics; instead, detoxification mechanisms have evolved
that lead to the formation of water-soluble conjugates that are
compartmented in the vacuole or deposited in the apoplast. The residues
may persist in plant tissues for a considerable time, and may affect
consumers of the plant tissues. A thorough understanding of the
metabolic fate of xenobiotics is therefore important.
✓ Genetic engineering of crops with plant or bacterial genes has already
produced transgenics that are resistant to herbicides and air pollutants. In
time, similar approaches may lead to workable strategies to develop the
phytoremediation of land polluted by industrial chemicals Plants can also
detoxify air pollutants, for example, ozone, which is increasing in the lower
atmosphere as a result of human activity.