III.

GLYCOSIDES

Glycosides  plant constituents which produce sugars upon hydrolysis

 Components:
Glycone Aglycone B. Cardiac Glycosides
(Genin)  have low margin of safety.
Sugar component Non-sugar component *Toxicity is more likely in the presence of Hypokalemia.
Common denominator Basis for classification   Test for Cardiac Glycosides:
Inactive Therapeutically active - Baljet’s Test
 (Beta) – only form of Glycoside that occurs in plants - Legal’s Test
 yield sugars as product of hydrolysis - Keller-Keliani’s Test
 are condensation product of sugar w/ various organic aglycone: steroidal
hydroxyl compounds  test: Lieberman- Bustard Test
 has beta--D-glucose as its most frequently occurring sugar Salkowski Test
 C, S, N; O – glycosides Cardenolides Bufadienolides
”sugar ether” (R-O-R) More common Less common
 Ether Bond From toad skin (Bufo spp.)
Anthocyanins  pigments of flowers which is of Glycosidic Optimum activity Less activity
character C23 C24
Glycone: 2 deoxysugar
Test: Keller-kellani test
A. Anthraquinone Exert action on the cardiac
 Aglycone: Anthraquinone  Borntragers test muscles:
 derivatives are colored orange-red + inotropic -cardiac
 Penicillium islandium –used to study these glycosides contractility
 commonly used as cathartics chromotropic - cardiac
1. Cascara Sagrada  sacred bark (Rhamnus Purshianus) rate
 Cascaroides A,B – optical isomers of Barbaloin MOA: Na-K ATPase pump
C,D – optical isomers of Chrysaloin USE: for Heart Failure
– has reduced
 Lane’s pills: Casanthrol 1. Digitalis fox glove (D. purpurea)
cured with MgO x 1yr  Grecian Foxglove (D. lanata)
Magnesium oxide – used to treat Cascara Constituents:
Sagrada Extract to reduce ▪Digoxin  water soluble
its bitter taste.  easy to control in TDM
2. Frangula  Blackthorn bark (Rhamnus frangula) (Therapeutic Drug Monitoring)
 Movicol = Frangula + Karaya Gum  0.5 to 2 mg/mL
3. Aloe – dried latex or juice of the leave of: ▪Digitoxin  lipophilic
Curacao Aloe: A. barbadensis, A. vera  computely absorbed
Cape Aloe: A. spicata, A. ferox  most powerful glycoside for digitalis
 constituents:  most lipid-soluble of the cardiac glycoside
 chief principle: used in therapeutics
-barbaloin (Aloin A)  long half-life (increase for toxicity)
-Isobarbaloin (Aloin B)  1 digitoxigenin – aglycone
 aloin  C-glycoside 3 digitoxone – glycone
aloe-emodin  O-glycoside ▪Des-acetyllanatoside (Deslanoside)
Uses: Cathartics initial rapid loading of digitalis
Pharmaceutical aid in compound Benzoin Tincture digitalization
Management of burn wounds (Aloe vera gel) Deslanoside is more soluble than Lanatoside
4. Rhubarb – dried rhizome/ root 2. Convallaria  Lily of the Valley (C. majalis)
Chinese/medicinal – Rheum officinale, R. palmatum convallatoxin
Ornamental – R. rhaponatum 3. Apocymum  Black Indian hemp (A. cannabinum)
Indian/ Himalayan – R. emodi, R. webbianum
cymarin
 Principal Constituent: Rhein Anthrone 4. Adonis – Pheasant’s Eye (A. vernaliz)
5. Senna (Senokot®) – cultivated on lands resembling rice paddies  adonitoxin
 dried leaflets of 5. Cactus Grandi florus – Night blooming cereus
tinnevelley senna – whole leaves of (Selenereus grandiflorus)
Cassia Angustifolia 6. Black Hellebore – Helle borus niger = Christmas nose
alexandria senna – broken leaves of  hellebrin
Cassia acutifolia
7. Strophantus – S. kombe, S. hispidus, S. gratus, Acokanthera shimperi
contains Senosides A & B K- Strophantin – less toxic
Sennoside is amore potent laxative than G-Strophantin  toxic form (Ouabain)
Cascara Sagrada 8. Squill bulb – Mediterranean/ White Squill: Urginea maritima
6. Chrysarobin  mixture of neutral principles  Indian: Urginea indica
from Goa powder (Andira avaroba) Sullarenin - bufadenolide
Hot Benzene– is used to extract 50-70% yield
Chrysarobin from Goa powder
Not a Cathartic, keratolytic, when dissolve in benzene
C. Cyanophore/ Cyanogenic Glycosides
cyanogenic = produce CN upon hydrolysis E.Isothiocyanate Glycoside
 rosaceous plants (Rosacease)  mustard glycosides
 Test: Guignard Test  glucosinolate
 Amygdalin – most common cyanophore glycosides  Cruciferus plants (Brassicaceae)
 Emulsin – composite enzyme (found in almonds; causes  extracted via Expression
 cause hydrolysis of -glucoside 1. Black Mustard – Sinapis Nigra
 Brassica Nigra
Amygdalin Sinigrin Myrosin Allyl Isothiocyanate
Amygdalase  (mustard volatile oil)
Prunasin 2. White Mustard – Sinapis alba
Prunase   Brassica alba
Mandelonitrile  less volatile
Amygdalin  hydrolyzed into Glucose, Benzaldehyde, & Sinalbin Myrosin Acrinyl Isothiocyanate
Hydrogen Cyanide pungent –tasting oil
Vitamin B17 (aka Amygdalin)
 flavoring agent
 useful for SCA (sickle cell anemia) F. Flavonol Glycosides
 Laetrile (Vitamin B17)  aglycone: Flavonoids
Amygdalin  yellow pigment: rutin, quercitin
Anticancer claims  citrus bioflavanoids: hesperidin, hesperitin, haringen
Sources: Cherry – Prunus serotina  common colds
Apricots – Prunus armeniaca  are abundant in the ff plant families:
Almonds – Prunus amygdalus - Polygoneaceae
Barley – Hordeum Vulgare - Rutaceae
- Umbelliferae
 Vitamin P – permeability factor
D. Saponin Glycosides  rutin + hespiridin
 bitter acid taste; from colloidal solutions in water  treat capillary fragility
froth upon shaking: ID test – Froth Test  Elin (Ulmus sp.) – quercitin
Other tests: Hemolysis Test  Milk thistle (Sylibum marianum) hepatoprotectant
Capillary Tube Test Silibium (treatment of liver ailments)
stermulatory = irritate mucosal membranes Sylimarin
 lyse RBS (especially in Cold-blooded animals)  Ginkgo biloba (G. biloba)
Test: Blood agar plate hemolysis test Ginkgolides, bilobalides
aglycone steroidal sapogenins: memory enhancer
neutral or acidic has a drug-herb interaction w/ ASA
Liebermann-Burchard’s test
Precursor for Steroids Synthesis
 two types based on their Sapogenins or aglycones: G. Alcohol
-Neutral Saponin – are derivatives of steroids 1. Salicin– Saligenin + D-glucose
-Acid Saponin – possess triterpenoid structures (salicin alcohol)
1. Glycirrhiza  Spanish licorice: Glycirrhiza glabra produced by the hydrolysis of Salicin by Emulsin
Russian licorice: G. glabra variety – Glandu lifera Salicin Emulsin Saligenin + -D-glucose
 glycyrrhizin, glycirrhizic acid  Willow bark (Salix purpurea)
 sweeteners; flavorant (Salix fragilis)
 disguise the bitter taste of Quinine by paralyzing the  Antirheumatic, anti-inflammatory
taste buds. 2. Populin  Poplar Bark (Populus spp.)
 demulcent; expectorant
 anti-inflammatory properties: PUD
-Peptic ulcer disease H. Aldehyde
Addison’s Disease 1. Vanilla  Vanilla planifolia: Mexican vera cruz
-decrease hormone Bourbon vanilla
production
Vanilla tahitensis: Tahitian vanilla
 Contraindicated w/ CHF (congestive heart failure)
 Vanillin as Glucovanillin or
& HTN (hypertension)
Glucovanillic acid
it cause Na & H2O retention
 Flavoring Agent
2. Dioscorea – Mexicom vam (Dioscorea floribunda)
 Synthetic analogue ethylvanillin
 Diosgenin: Anti-inflammatory,
precursor for steroids synthesis
 botogenin, hecogenin
3. Agave (A. cantalla) – fiber, hecagenin, manogenin, gifogenin
molluscide
4. Similax – Sarsa pogenin; smilagenin
5. Strophantus – sarmantogenin
6. Ginseng – source: American – Panax quinquefolus
Asian – Panax ginseng
 Panoxosides, Gensenosides, Chikuse/ susaponins
 adaptogen
I. Lactone Glycosides
1. Coumarin  lactone of -hydroxycinnamic acid
 fragrant odor, bitter aromatic, burning taste
 Tonka Beans (Dipterex adorata)
 flavoring agent
2.Bishydoxy coumarin/ Dicumarol
 improperly cured leaves of sweet clover Melilotus officinalis
 first oral anticoagulant, precursor of warfarin
3. Cantharide  Spanish/ Russian/ Blistering Flies
(Cantharis vesicatoria)
 Cantharidin – Vesicating principle
 Irritant, vesicant  remove warts
urgenital tract priapism
 aphrodisiac
4. Psoralens  Photosensitizing furocoumarin
 Family: Rutaceae & Apiaceae
 Bishop’s Flowers – Ammi majus
 Methoxsalen : Xanthotoxin
 Uses: Repigmentation in vertigo
For symptomatic psoriasis
5. Santorin  Artemisia cing, Amaritima
 Antihelminthic, Toxic
6. Isoflavones  Soybean (Glycine soja)
 phytoestrogens – bind to estrogen receptors
alleviate menopausal symptoms
7. Skimmin
8. Aesculin

J. Phenol Glycosides
1. Uva ursi  Bearberry ( Archtostaphylo uva ursi)
Arbutin
available in the form of herbal teas
 diuretic, astringent
2. Poison- Ivy & Oak  Rhus spp.
Urushiol  a non-volatile principle producing
allergic symptoms
– cause delayed contact dermatitis

(Other) Phenol glycosides:

Arbutin (from uva ursi)
Hesperidin (from citrus fruits)
Phlrodzin (from root barks of rosaceous plants)
Baptisin (from Baptisia)
Iridin (from Iris Species)
IV. Tannins
Tannins  non-crystallizable hydrocolloid mixture of polyphenols
 amorphous, polyhydroxy-phenolic compounds
 form colloidal solutions in water
 acid puckering taste (astringent taste)
 precipitated by Cu, Pb, Cr2O72
 precipitated gelatin, alkaloids
 astringent – precipitate proteins
 carcinogenic potential
 alkaloidal Antidote
 groups of compounds that make s wood darker in color
 produced Deep Red w/ Potassium Ferricyanide & Ammonia
 animal hide tanningleather

tannins
Hydolyzable Non-hydrolyzable
Other names Pyrogallotannins Phlobatanins
condensed
Hydrolytic Pyrogallol X
products (given soluble Phlobaphenes
compounds w/ red polymerization
lead acetate) products
FeCl3 Blueblack Greenblack
Leather Type Bloom Leather Tanner’s Red
Br2 () (+)

 Hydrolyazable Tannins  consist of gallic acid or related polyhydric

compounds esterified w/ glucose
 Nonhydrolyzable Tanninc  most result from the condensation of 2 or
more polyhydric compounds esterified w/
glucose

1. Hamamelis  Witch Hazel leaves (Hamamelis virginiana)

 hamamelitannin
 astringent, hemostatic
hemorrhoidal preparations
insect bites & stings
teething preparations
2. Nutgall  hardened excrescence from the
young twigs of Quercus infetoria,
when a hymenopherous insect (Cynips tinctora) bores
holes to deposit ova
Tannic Acid (Gallotannic Acid)  is a mixture of esters of
gallic acid w/ glucose
principal constituent of Nutgall
used as astringent
 components of Universal Antidotes:
1. MgO – neutralize acid
2. Tannic acid – precipitate alkaloids
3. Activated Charcoal – adsorp poisons
3. Japanese & Chinese Galls – Rhus chinensis ; gallic acid
4. Apple  tannin-rich plant used in medicine as Astringent.
 Pyrus mallus