Topic;
Cyanogenic Glycosides
Ghulam Murtaza M . Adeel
Reg #; 2014-UAM-138 2014-UAM-164
Department of Entomology
M.N.S. University of Agriculture
Multan
Introduction
Cyanogenic glycosides (CGs) are nitrogen-containing secondary metabolites
whose biosynthetic origin is similar to that of glucosinolates.
Intermediately polar, water-soluble compounds that often accumulate in the
vacuoles of plant cells.
These compounds are usually O-b-glycosides of cyanohydrins (a-
hydroxynitriles).
Cyanogenic glycosides are formed in the cytoplasm but stored in the central
vacuole.
More than 75 different cyanogenic glycosides occur among plants.
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Tiger beetles, millipedes, and centipedes are able to use cyanogenic glycosides as a
defense against predators. These insects sequester the cyanide in their cells. When an
insect is attacked by a predator, cyanide is released as a defense.
It is estimated that between 3000 and 12,000 plant species produce cyanogenic
glycosides.
Many important crop plants are cyanogenic, including sorghum, almond, lima
bean, and white clover. Many bacteria and fungi are cyanogenic.
Occurrence
Cyanogenic glycosides have been reported from atleast 2650 plants belonging to
more than 550 genera and 130 families.
Cyanogenic plant species include ferns, gymnosperms, monocotyledonous and
dicotyledonous plants.
The important families in which cyanogenic glycosides commonly occur are
Araceae, Asteraceae, Euphorbiaceae, Fabaceae, Flacourtiaceae, Maleesherbia,
Proteaceae, Rosaceae, Sapindaceae, Turneraceae, Compositae, Gramineae, and
Leguminoseae.
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Different glycosides occurred in different plant parts e.g prunasin is found in the
vegetative portions and amygdalin is found in the seeds of Prunus species.
Several cyanogenic glycosides co-occur in the same plant tissues. Both mono- and
diglycosides co-occur in flax (Linum usitatissimum) and in rubber (Hevea
brasiliensis) (23,30). Complex mixtures of di-, tri-, and tetraglycosides occur in
members of the family Asteraceae.
Plants Having Cyanogenic glycoside
Plants Major cyanogenic glycoside present
Cassava (Manihot esculenta) - root Linamarin
Sorghum (Sorghum vulgare) – leaves Dhurrin
Flax (Linum usitatissimum) – seed meal Linamarin, linustatin, neolinustatin
Bamboo (Bambusa arundinacea) – young Taxiphyllin
shoots
Apple (Malus spp.) – Seed Amygdalin
Peach (Prunus persica) – Kernel Amygdalin
Apricot (Prunus armeniace) – Kernel Amygdalin
Plum (Prunus spp.) – Kernel Amygdalin
Cherry (Prunus spp.) Amygdalin
Bitter almond (Prunus dulcis) Amygdalin
Classification
Most cyanogenic glycosides are derived from five protein amino acids, others from
the nonprotein amino acid 2-(2-cyclopentenyl)glycine and from nicotinic acid. The
important classes of cyanogenic glycosides include those derived from;
Phenylalanine
Tyrosine and Leucine
Valine and isoleucine
Leucine and Cyclopentenylglycine
Fatty acids (cyanolipids)
Nicotinic acid
Nitroacids and nitroalcohol
Tyrosine nitrile glycoside
Cyanogens Derived from Phenylalanine
Several cyanogenic glycosides are derived from L-phenylalanine.
These cyanogens are found in the Rosidae and Asteridae.
The important compound of this group is amygdalin, which is widespread in seeds
of members of the Rosaceae, such as apples, peaches, cherries, and apricots.
Asteraceae, Fabaceae, and Rosaceae.
Cyanogens Derived fromTyrosine
Cyanogens derived from tyrosine such as dhurrin, taxiphyllin, and triglochinin are
widespread in nature.
Tyrosine-derived glycosides most commonly occur in monocotyledonous
angiosperms and in the Magnolidae.
Dhurrin present in sorghum leaves.
Plants Having Cyanogenic glycoside
Plants Major cyanogenic glycoside present
Cassava (Manihot esculenta) - root Linamarin
Sorghum (Sorghum vulgare) – leaves Dhurrin
Flax (Linum usitatissimum) – seed meal Linamarin, linustatin, neolinustatin
Bamboo (Bambusa arundinacea) – young shoots Taxiphyllin
Apple (Malus spp.) – Seed Amygdalin
Peach (Prunus persica) – Kernel Amygdalin
Apricot (Prunus armeniace) – Kernel Amygdalin
Plum (Prunus spp.) – Kernel Amygdalin
Cherry (Prunus spp.) Amygdalin
Bitter almond (Prunus dulcis) Amygdalin
Cyanogens Derived from Leucine
The most widespread cyanogenic glycosides in this group are linamarin and
lotaustralin.
Including the other less common glycosides epilotaustralin, linustatin,
neolinustatin, and sarmentosin epoxide, which are mostly encountered in the species
of the Asteraceae and Linaceae.
The gentibiose derivative linustatin and neolinustatin are found in flax seed.
Cyanogens Derived from Leucine
Several cyanogenic glycosides arising from leucine have restricted distribution.
Glycosides such as proacacipetalin, epiproacacipetalin, and proacaciberin are
known only from the genus Acacia.
Heterodendrin and epiheterodendrin occur only in the Sapindaceae (lychae) and in
the Poaceae (grasses).
Cyanogens Derived from Valine and
Isoleucine
The most widespread cyanogenic glycosides in this group are linamarin and
lotaustralin.
Including the other less common glycosides epilotaustralin, linustatin,
neolinustatin, and sarmentosin epoxide, which are mostly encountered in the species
of the Asteraceae, Euphorbiaciae, Fabaceae, and Linaceae.
The gentibiose derivative linustatin and neolinustatin are found in flax seed and
Rossiflora species
Cyanogens Derived from Cyclopentenylglycine
The nonprotein amino acid 2-(2-cyclopentenyl)glycine yields several cyanogenic
glycosides that contain a cyclopentenoid ring structure.
These compounds include decidaclin, tetraphyllin A, tetraphyllin B, volkenin,
gynocardin, and other cyanogens.
These compounds occur in the families Flacourtiaceae, Turneraceae and
Achariaceae.
Cyanolipids
Cyanolipids are derivatives of a leucine-derived cyanohydrin
Found in the seed oils of several species of the family Sapindaceae.
Cyanogens Derived from Nicotinic Acid
The cyanogenic lipid acalyphin from Acalypha indica from Euphorbiaceae is
derived from nicotinic acid.
Nitroglycosides
Several plant families contain the glycoside of nitroacids and nitroalcohol.
Several esters of 3-nitropropionic acid occur in the genera Astragalus, Coronilla,
Indigofera (Fabaceae), Heteropteris, Hiptage (Malpighiaceae), Viola (Violaceae), and
Corynocarpus (Corynocarpaceae).
Nitrile Glucosides
Nitrile glucosides are noncyanogenic compounds having structural similarities to
intermediates in cyanogenic glycoside biosynthesis.
These compounds are found in members of the Simmondsiaceae, Aquifoliaceae,
Menispemaceae, Fabaceae, Boraginaceae, Ranunculaceae, and Crassulaceae families.
BIOSYNTHESIS
The biosynthesis of the L-tyrosine-derived cyanogenic glycoside dhurrin has been elucidated
in sorghum.
Studies carried out using microsomes prepared from etiolated cassava seedlings demonstrate
the involvement of the same classes of intermediates as in sorghum.
The extreme lability of the N,N-dihydroxyamino acid makes it impossible to investigate
directly since it can be neither chemically synthesized nor isolated. Microsomal activity is
dependent on the presence of oxygen and NADPH.
The conversion of tyrosine to the p-hydroxymandelonitrile proceeds with the consumption of
three molecules of oxygen, indicating the involvement of three hydroxylation reactions.
Two molecules of oxygen are consumed in the conversion of tyrosine to the aldoxime, whereas
a single oxygen molecule is consumed in the conversion of the aldoxime to the cyanohydrin.
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The whole pathway from the parent amino acid to the cyanogenic glycoside is catalyzed by
three enzymes.
Two are multifunctional cytochrome P450s and the third a UDPG-glucosyltransferase.
The first committed steps in the biosynthesis of cyanogenic glycosides are the conversion of
amino acids to the corresponding oximes.
The final step in the biosynthesis of dhurrin in sorghum is transformation of labile
cyanohydrin into a stable storage form by glucosylation of (S)-p-hydroxymandelonitrile at
the cyanohydrin function.
The UDP-glucose:p-hydroxymandelonitrile-O-glucosyltransferase was isolated from
etiolated seedlings of sorghum. Glucosyltransferases have been isolated and purified from a
few cyanogenic species.
BIOACTIVITY
One of the most probable explanations of the biological role of cyanogenic
glycosides in some plants is the participation in defense mechanisms against different
phytopathogens, despite the fact that both plants and animals possess the ability to
detoxify cyanide.
Larvae of Spodoptera eridania prefer to graze on CG-containing plants and grow
better when cyanide is present in their diet.
Studies have shown that CGs can act as feeding deterrents or phagostimulants,
depending on the insect species .
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Malagon and Garrido (74) concluded that bitter almond plants are resistant to
larvae of buprestid Capnodis tenebrionis, owing to the high concentration of CGs.
The CG of cassava tubers improved its resistance to the cassava root borer.
The level of cyanide in the leaves of the grass, especially after defoliation by
armyworm larvae, were high enough to kill cattle, although the larvae themselves
appeared unaffected.
MECHANISM OF ACTION
Plants containing cyanogenic glycosides usually contain b-glycosidases capable of
removing glucose or sugar from cyanogenic glycoside to produce a cyanohydrin
(aglycone).
A second enzyme, hydroxnitrile lyase, catalyzes the dissociation of the cyanohydrin to a
carbonyl compound (an aldehyde or a ketone) and hydrogen cyanide.
Naturally the substrate and enzymes are compartmentalized within the plant and the
cyanide release occurs only when the plant is damaged.
The HCN produced is a highly toxic substance that inhibits cytochrome oxidase and
other respiratory enzymes.
It has also been shown that dhurrin, a cyanogenic glycoside, act as an oviposition
deactivator for the pests.
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Some insects produce cyanogenic glycosides de novo while a few other insects
sequester cyanogenic compounds from plants.
The genus Heliconius, which feeds on Passiflora species, has evolved alternate b-
glycosidases that inhibit hydrolysis of the cyanogenic glycoside.
