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Secondary metabolites
•Glycosides
•Tannins
•Alkaloids
І. Glycosides - the sugar (glycoside) and the non-sugar
(aglycone) moieties.
glucosidases
glycoside
Sugar residue (glycol) + aglycone
Glycosides types :
1.
Anthraquinone
2.
Phenolic
3. Pigment
4. Coumarin
5. Cardio glycosides
6. Saponins
7. Iridoids
8. Tioglycosides
9. Cyanogenic
1. Anthraquinone glycosides - with aglycone anthracene and its derivatives
-
Aloe - emodin (Aloe vera - Aloe,
Liliaceae)
-
Rheine (Rheum officinale - Rhubarb
Polygonaceae)
-
Hypericin (Hypericum perforatum - St.
John's wort, Hypericaceae)
-
Chrysophanol (Senna obtusifolia senna, Fabaceae)
Action: they are the stimulant cathartics
and exert their action by increasing the
tone of the smooth muscle in wall of the
large intestine.
2. Phenolic glycosides - with aglycone benzene ring combined with an
alcohol.
Gallic acid - in bark of oak (Quercus sp.,
Fagaceae), leaves of tea (Thea sinensis,
Theaceae), tanning sumac - Rhus coriaria,
Anacardiaceae)
Structural formula of
phenol
Caffeic acid - in the resin of coniferous,
poplar buds
ellagic acid
Ellagic acid - Rubus idaeus
(raspberry, Rosaceae), R.
caesius (blackberry)
Salicylic acid - bark of white
willow (Salix alba, Salicaceae)
Arbutin - bearberry (Arctostaphyllos uva-ursi, Ericaceae Family)
Eugenol – clover genus Trifolium (Fabaceae Family)
Gossypol - cotton (Gossypium hirsutum, Malvaceae Family)
Action : antiseptic, anthelminitic &
caustic activity
3. Pigment glycosides - flavonoids and anthocyanins
Flavonoids glycosides (flavonoids) - with aglycone flavone or
isoflavone gives yellow color of plant parts
Action: antioxidant, anti - inflammation, antibacterial, cardiovascular diseases inhibit coagulation and thrombus formation
Anthocyanins (anthocyans) - with aglycone anthocyanin
• a subgroup of flavonoids, which give plants their distinctive
colors - blue to violet
• present in the vacuolar sap of the epidermal tissues of
flowers and fruit
• formation depends on the breakdown of sugars in the
presence of bright light
• found In flowers & fruits - to atract pollinators and eaters
• in photosynthetic tissues (leaves and stems) - a
"sunscreen", protecting cells from high-light damage by
absorbing blue-green and ultraviolet light, thereby protecting
the tissues from photoinhibition (high-light stress).
•
Cyanidin - grapes, blueberries, cherries
Malvidin – common mallow (Malva sylvestris,
Malvaceae)
Delphinidin – larkspur (Consolida regalis,
Ranunculaceae)
Pelargonidin – pelargonium (Pelargonium sp.,
Geraniaceae)
The sugar-free molecule - is
called anthocyanidins
Peonidin – peony (Paeonia peregrina,Paeoniaceae)
Action: increase the elasticity of capillary blood vessels - bleeding diuretic,
antispasmodic, stimulate Cardio Vascular System (CVS), antioxidants.
Autumn coloration (including red) - the result of
breakdown of green chlorophyll, which unmasks the alreadypresent orange, yellow, and red pigments
(carotenoids, xanthophylls, and anthocyanins).
4. Coumarin glycosides - with coumarin aglycone
Coumarin - green shield bug (Anthoxantum
odoratum, Poaceae), lady's bedstraw (Galium
odoratum, Rubiaceae)
Dicoumarol - Sweet clover (Melilotus alba & M.
Officinalis – Fabaceae)
Psoralen – fig (Ficus carica, Moraceae), parsley
(Apium graveolens, Apiaceae)
Pastinatsin, Bergapten – parsnips (Pastinaca
sativa, Apiaceae)
Umbelliferone – carrot (Daucus carota,
Apiaceae), coriander (Coriandrum sativum,
Apiaceae)
Aesculin – in the bark of Aesculus
hippocastanum – horse chesnut
(Hippocastanaceae)
Coumarin molecule
Action:
•protect skin from UV light
•Anticoagulant – inhibit hepatic
synthesis of vitamin K-dependent
coagulation factors
• antifungicidal properties
5.Cardiac glycosides – increase cardiac output by increasing the force of
contraction of the cardiac muscle
Cardiac glycosides – types:
- Cardenolides:
• Strophanthin, ubain (Strophantus combe, Erythroxilaceae)
• Digitoxin, digoxin (Digitalis purpurea, Scrophullariaceae)
• Oleandrin (Nerium oleander, Apocynaceae)
• Convalozid, Convalatoxin (Convallaria majalis, Liliaceae)
• Adoni toxin (Adonis vernalis, Ranunculaceae)
• Periplocinum (Periploca graeca, Apocynaceae)
- Bufadienolides:
• Helleborine (Helleborus odorus, Ranunculaceae)
• Scilaren (Allium maritimum, Liliaceae)
Action: diuretic, emetic, insecticide
• Initial inhibition of potassium sodium (K/ Na)
ATPase - increasing on intracellular sodium (Na)
concentration
3 Na = 1Ca
• Secondary activation of potassium - sodium –
exchange pump in the cell membrane
• increase the concentration of intracellular free
6. Saponin glycosides (saponins)– with sapogenin aglycone(С27)
or triterpene (С30).
Molecule of sapogenin
Saponins types:
Steroidal saponins:
Ruskogenin - mouse thorn (Ruscus aculeatus, Liliaceae)
Diosgenin– Dioscorea sp. (Dioscoreaceae), Trigonella sp.
(Fabaceae)
Usage: the basis for the synthesis of steroid hormones and
derivatives of cortisone
Triterpenic saponins:
- Aescin - horse chestnut (Aesculus hippocastanum,
Hyppocastanaceae)
-
Saporubin - soapwort (Saponaria officinalis, Caryophyllaceae)
-
Glycyrrhizin - liquorice (Glycirhiza glabra, Fabaceae)
-
Primula saponin - Primrose (Primula officinalis, Primulaceae)
-
Header saponin – ivy (Hedera helix, Araliaceae)
-
Panax saponin - Ginseng (Panax ginseng, Araliaceae)
Action: expectorant
7. Iridoid glycosides - with aglycone iridoids (С10).
Iridomyrmex purpureus
Iridoid molecule
Types of iridoid glycosides:
Aucubin - Plantain - Scrophulariaceae family (Plantaginaceae)
Harpagoside - Lamiaceae family (Lamiaceae)
Amarogentin, gentiopicrin (secoiridoids) - Gentianaceae family
(Gentianaceae)
Valtrate, isovalerate (valepotriats) - Valerianaceae family (Vallerianaceae)
Asperulozid - Rubiaceae Family
Action: appetite exciting, sedative,
anti-inflammatory
8. Tioglycosides – sulfur containing glycosides
Mustard glycosides - Brassicaceae family
Sinalbin - white mustard
(Sinapis alba)
Sinigrin - black mustard (Sinapis nigra)
Action: bile eviction, appetite exciting, diuretic, expectorant
9. Cyanogenic glycosides – with aglycone cyanide group
Hydrogen cyanide – final
product of cyanogenic
glycosides degradation
A cyanide group - construction
Amygdalin - in representatives of
Rosaceae family - cherry, almond,
apricot, apple
Prunazin - Scrophulariaceae family (Scrophullariaceae)
Sambunigrin – Rubiaceae family (Rubiaceae) – Sambucus nigra
Linamarin– Linaceae family (Linaceae)
Durin– Poaceae family (Poaceae) – Sorghum bicolor
Inflorescence of Sambucus nigra
Contents of Cyanicogenic glycosides in
Eucalyptus globulus leaf
Action: laxative, sedative, antitumor
ІІ. Tannins - complex nitrogen- free organic compounds with
many hydroxyl groups
Molecule of tannic acid
Basic property of tannins precipitation of proteins
Types of tannins:
1.Hydrolyzable tannins - with a strong astringent action
1а. Gallotannins – Gallic acid , digallic acid
1 b. Ellagotanins - leaves of sumac, madder, alder, walnut, oak and oak galls
2. Condensed tannins – catechins and gallocatechins
Acacia catechu (Fabaceae Family)
Plant sources of catechin tannins - strawberry leaves,
persimmon, pomegranate, hazelnuts;
- fir bark, acacia, chestnut;
- coffee, tea, wine , beer, chocolate
Action:
• antibiotic
• herbicide
• inflammatory factor
• nutritional supplement - E 181
* Catechin tannins accumulate in large quantities in the meristem cells of the
roots of certain species to inhibit the growth of neighboring species - allelopathy
! The tannins are easily connected with ions of metals (Fe +) - iron
deficiency anemia
Roots and bark of plants - sources of
tannin
Freshwater dolphins in tannins
saturated waters of the
Amazon River
ІІІ. Alkaloids - nitrogen-containing organic compounds of alkaline nature. They
are synthesized from amino acids or organic acids.
Types: true proto alkaloids and pseudo alkaloids
1. True alkaloids:
• Pyridine
• Piperidine
• Tropane
• Quinoline
• Isoquinoline
• Quinolizidine
• Indole
True alkaloids - with N in the main chain, formed from amino acids
• Pyridine alkaloids
nicotine, anabazin - tobacco (Nicotiana tabacum, Solanaceae);
trigonelline - fenugreek (Trigonella foenum – graecum, Fabaceae)
• Piperidine alkaloids - with saturated heterocyclic ring, i.e., piperidine
nucleus .
Poison hemlock Conium maculatum
(Apiaceae)
Sedamin - yellow sedum (Sedum acre, Crassulaceae)
Lobeline – Lobelia inflata (Campanulaceae)
Piperine - black pepper (Piper nigrum, Piperaceae)
Isopeletierin– pomegranate (Punica granatm, Punicaceae)
Sedum acre
Lobelia inflata
• Tropane alkaloids
Tropane molecule
Atropine group - solanine, atropine, scopolamine, hyoscyamine – Solanaceae
family – potato, datura, belladonna, henbane.
Action: sedative, anticonvulsant, pesticide
Cocaine group - cocaine, ecgonine – Erythroxylaceae family - leaves of the
coca bush (Erythroxylon coca)
Action: strong CNS stimulant, local anesthetic
• Quinoline alkaloids -
Quinoline alkaloids such as quinine can be derived from amino acid L-tryptophan:
Echinopsin - globe thistles (Genus Echinops , Asteraceae)
Dictamin - Gasplant (Dictamnus albus, Rutaceae)
Quinine, cinchonine - Cinchona (Cinchona succirubra, Rubiaceae)
Application of quinine
Quinine molecule
Action: antipyretic, tonic, antimalarials
• Isoquinoline alkaloids
• Opium group - papaverine, morphine,
codeine, thebaine, glaucine, helitropin,
chelidonine,
protopin,
berberine,
sanguinarine – Papaveraceae family
• Amarilide group galantamine,
nivalin, likorin - Amaryllidaceae family
Action: treat atony to digestive canal
and uterus, paresis and paralysis,
antidote to curare
• Curare alkaloids
alferin, toxiferin
–
Strychnos toxifera
Action - a muscle relaxant
tubocurarine,
Strychnos toxifera – Loganiaceae
Family
Quinolizidine alkaloids - they are nitrogen-containing
heterocyclic compounds.
lupine, cytisine, sparteine - genus Laburnum, Cytisus,
Sophora (Fabaceae family) – nicotine acetylcholine receptor
agonist
• Action: medically used to help with smoking cessation
• Indole alkaloids - containing a structural moiety of indole; many
indole alkaloids also include isoprene groups and are thus called
terpene indole alkaloids.
• Loganiaceae Family
Strychnine, brucine - Strychnos nux-vomica (Strychnine tree)
Action: neuro stimulating, anesthetic, a muscle relaxant
•Apocynaceae Family
Reserpine - indian snakeroot (Rauwolfia serpentina)
•Action: hypertension and neuro - mental disorders treatment, insanity,
snakebite, cholera, central nervous system stimulator.
•Vincaceae Family
Vinca alkaloids: vincamine, vincarpin, vinblastine, vincristine Genus Vinca (Periwinkle) – anti - mitotic and anti-microtubule agents - used
in chemotherapy for cancer - inhibiting the ability of cancer cells to divide.
•
Serotonin = phytoserotonin :
- in fruits - serotonin regulates intestinal activity, its presence of plants
may serve as a way of ensuring seeds are passed through and
expelled by the digestive tract quickly - laxatives effect.
- In drying seeds- helps to dispose of accumulating ammonia.
Another functions:
•Growth regulation
•Xylem sap exudation
•Flowering
•Ion permeability
•Plant morphogenesis
•Regulation of ripening
Sources: walnuts, hickory,pineapples, banana, kiwi fruit, plums and tomatoes,
spines of stinging nettles
Proto Alkaloids - with N in the side chain
Ephedrine (Ephedra sinica)
Action - a stimulant, appetite suppressant,
amphetamine replacement
+
+
=
• Mescaline – Lophophora williamsii (Cactaceae), Acacia berlandieri
(Fabaceae)
Action - psychedelic (cause hallucinations, penetrating)
Colchicine alkaloids
• Colchicine, colchamin – Liliaceaefamily – supress cell division
Colchicum
automnale
Pseudo Alkaloids - not formed from
amino acids
Types:
• terpene
• steroid
• purine alkaloids
Delphinium fussum
•Terpene alkaloids
Aconitine grupe
aconitine - larkspur (Ranunculaceae family) – strong neurotoxins used as a local
anesthetic
Action: can interact with the voltage-dependent sodium-ion channels in the cell
membranes of excitable tissues - cardiac, skeletal muscles and neurons \
Results: paresis & paralysis
• Steroid alkaloids
- cyclopamine, veratramine - California corn lily (Veratrum californicum Liliaceae Family)
- solanidine, chaconine, tomatidin - Solanaceae Family
Action: suppress cell division, metabolic exchange, hormone replacements
• Purine alkaloids – caffeine, theobromine, theine, theophylline (coffee, tea,
leaves and cola nuts)
Metabolism of caffeine in the liver
Structural analogy of the molecule of caffeine with aglycone of
adenosine – adenine = antagonist of adenosine receptors
Action: excite CNS and CVS
Effects of caffeine on spider
Action: psychostimulant