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BIOLOGICALLY ACTIVE COMPOUNDS
IN PLANT RAW MATERIALS
PRIMARY METABOLITES:
carbohydrates
amino acids, peptides, proteins
lipids
nucleic acids
chlorophyll
SECONDARY METABOLITES:
glycosides
alkaloids
essential oils
tannins
bitter compounds
etc.
PRIMARY METABOLITES:
CARBOHYDRATES
Monosaccharides
Glucose, fructose, rhamnose, arabinose – constituents of numerous glycosides and polysaccharides
Digitoxose (deoxyrhamnose) – component of cardiac glycosides of foxglove (Digitalis sp.)
Oligosaccharides – consist of 2-10 monosaccharides
Rutinose (rhamnose + glucose) – component of rutin=rutoside (quercetin-3-rutinoside)
obtained from buckwheat (Fagopyrum esculentum) herb
Polysaccharides – consist of ≥ 10 monosaccharides
Starch
Celulose
Inulin – storage polysaccharide in the roots of plants from the family Asteraceae,
e.g. elecampane (Inula helenium), Jerusalem artichoke (Helianthus tuberosus),
common dandelion (Taraxacum officinale);
– sweetener for diabetes
– prebiotic
– source of fructose
Polysaccharides with immunomodulatory activity
– e.g. in purple coneflower (Echinacea purpurea) herb, aloe (e.g. Aloë arborescens) leaf,
European goldenrod (Solidago virgaurea) herb, common dandelion (Taraxacum officinale) flowers
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Mucilages – mixtures of polysaccharides
- occur in special cells or reservoirs
- in water form slippery colloidal dispersions
- activity: coating, protecting, demulcent, soothing, mildly laxative
- internally used – in irritation and inflammations of mucous membranes
of gastrointestinal tract (they are not absorbed and act locally)
and respiratory tract (dry irritating cough)
- externally used – to alleviate skin irritation
Mucilage-containing raw materials: flax (Linum usitatissimum) seed,
fenugreek (Trigonella foenum-graecum) seed, marshmallow (Althaea officinalis) root,
black hollyhock (Althaea rosea var. nigra) flower, wool mullein (Verbascum densiflorum) flower,
ribwort plantain (Plantago lanceolata) leaf, psyllium (e.g. Plantago ovata, P. arenaria) seed,
coltsfoot (Tussilago farfara) leaf
PEPTIDES
R
CH
CO
NH
2
NH
CH
COOH
R
1
• dipeptides: consist of 2 amino acids
• oligopeptides: consist of 3-10 amino acids
• polypeptides: consist of > 10 amino acids
viscotoxins – in mistletoe (Viscum album) herb;
- injected subcutaneously cause necrosis of skin tumours
in shepherd’s purse (Capsella bursa-pastoris) herb – peptides with hemostyptic action
PROTEINS – polypeptides with molecular weight > 10 000
Simple proteins (composed of amino acids only)
Complex proteins, e.g.:
glycoproteins = proteins + carbohydrates
• glycoproteins with immunostimulatory activity – in purple coneflower (Echinacea
purpurea) herb, aloe (Aloë vera, A. arborescens) leaf
• lectins – in herb of mistletoe (Viscum album);
- agglutinate red blood cells
- agglutinate cancer cells
chromoproteins – proteins + pigments/metal ions
e.g. chlorophyll – obtained from stinging nettle (Urtica dioica L.) herb
peptide bond
by binding sugars in cell membranes
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LIPIDS
Simple lipids, e.g. fats (composed of triglycerides = esters of glycerol and fatty acids)
Complex lipids – e.g. phosphoglycerides (e.g. lecithin in soy seeds)
Plant fats (oils) contain mainly unsaturated fatty acids and have a liquid form.
PUFA – polyunsaturated fatty acids
EFA – essential fatty acids
Essential fatty acids:
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Biological activity of essential fatty acids:
constituents of cell membranes
take part in biosynthesis of prostaglandins, prostacyclins, thromboxanes, leukotrienes
take part in cholesterol transport
affect body immune resistance
important in prophylaxis of atherosclerosis
used in chronic skin diseases, allergic diseases, rheumatoid arthritis, disorders of central
nervous system (e.g. in supportive therapy of multiple sclerosis)
Plant oils rich in γ-linolenic acid:
evening primrose (Oenothera paradoxa, O. biennis) seed oil
borage (Borago officinalis) seed oil
black currant (Ribes nigrum) seed oil
H
3
C
COOH
H
3
C
COOH
H
3
C
COOH
linoleic acid
18:2, n-6
α-linolenic acid
18:3, n-3
γ-linolenic acid
18:3, n-6
soy oil,
sunflower oil,
evening primrose seed oil
flax seed oil
evening primrose seed oil,
borage seed oil,
black currant seed oil
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SECONDARY METABOLITES:
GLYCOSIDES
– consist of glycone (sugar moiety) and aglycone
Classification of glycosides in regard to the type of bond between glycone and aglycone:
O-glycosides
C-glycosides
S-glycosides
N-glycosides
Classification of glycosides in regard to aglycone:
flavonoid glycosides
anthocyanosides
saponosides
cardiac glycosides – cardenolide and bufadienolide glycosides
anthraglycosides
coumarin glycosides
phenolic glycosides
iridoid glycosides
sterol glycosides
glucosinolates
FLAVONOIDS
yellow pigments, occurring in vacuoles, esp. in aerial parts of plants (flowers, leaves)
occur as free compounds or as O-, rarely C-glycosides
Flavones – e.g. apigenin, luteolin
Flavone glycosides – e.g. vitexin (apigenin-8-C-glucoside) – in hawthorn (e.g. Crataegus
monogyna) inflorescence – improves coronary flow
Flavonols
e.g. quercetin, kaempferol, myricetin
Flavonol glycosides
e.g.
rutin (quercetin-3-rutinoside) – in buckwheat (Fagopyrum esculentum) herb,
rue (Ruta graveolens) herb, heartsease (Viola tricolor) herb,
black elder (Sambucus nigra) flower
- decreases capillary permeability
- antioxidant (e.g. prevents the oxidation of ascorbic acid)
hyperoside (quercetin-3-galactoside) – e.g. in St. John’s wort (Hypericum perforatum) herb,
birch (Betula pendula, B. pubescens) leaf
quercetin
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Isoflavones
genistein, daidzein – in soy seeds
– phytoestrogens; anti-cancer activity
Biflavonoids
bilobetin, ginkgetin – in maidenhair tree (Ginkgo biloba) leaf
– enhance coronary and brain flow
Flavonolignans
Silymarin (main compound – silybin) – in milk thistle (Silybum marianum) fruit
– anti-hepatotoxic, regenerating liver cells, anti-inflammatory action
Biological activity of flavonoids:
reducing blood vessel permeability and fragility
prevent bleeding, ecchymosis, varicose
veins, atherosclerosis
anti-aggregatory (inhibiting platelet aggregation)
antioxidant
diuretic
spasmolytic
anti-inflammatory
detoxifying – they chelate metal ions, e.g. Cu
UV-protecting
antiviral
Flavonoid-containing raw materials: field horsetail (Equisetum arvense) herb,
common knotgrass/knotweed (Polygonum aviculare) herb, birch (Betula pendula) leaf,
heartsease (Viola tricolor) herb, European goldenrod (Solidago virgaurea) herb,
lime (Tilia cordata, T. platyphyllos) inflorescence, black elder (Sambucus nigra) flower,
hawthorn (Crataegus monogyna ) inflorescence,
sandy everlasting (Helichrysum arenarium) inflorescence,
St. John’s wort (Hypericum perforatum) herb, chamomile (Matricaria chamomilla) flower head
O
OH
O
OH
O
H
genistein
amenthoflavone
bilobetin
ginkgetin
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ANTHOCYANINS
• plant pigments: pink-red-blue-violet
• usually occur as O-glycosides – anthocyanosides;
aglycone – anthocyanidin:
Biological activity of anthocyanins:
reducing capillary permeability and fragility
slightly diuretic
anti-inflammatory
anti-aggregatory
UV-protecting
antiviral
antioxidant
improving microcirculation in eye
improving visual acuity
Anthocyanin-containing raw materials:
bilberry (Vaccinium myrtillus) fruit, black elder (Sambucus nigra) fruit,
bluebottle (Centaurea cyanus) flower, black hollyhock (Althaea rosea var. nigra) flower
SAPONINS
triterpene saponins
steroid saponins
Biological activity of saponins:
they lower the surface tension of water solutions (
foaming)
facilitate dissolving and absorption of other active substances
haemolytic
lowering blood cholesterol level
expectorant (by irritating stomach mucous membrane)
diuretic
anti-inflammatory
antifungal
psychostimulant
immunomodulatory
chemopreventive
antioxidant
toxic for fish and other cold-blooded animals;
for mammals – when given parenterally;
some of them (e.g. saponins of Agrostemma githago, Cyclamen) – also after ingestion
Raw materials containing triterpene saponins: soapwort (Saponaria officinalis) root, cowslip
(Primula veris) root [e.g. primulasaponin A], liquorice (Glycyrrhiza glabra) root [e.g. glycyrrhizin],
horse chestnut (Aesculus hippocastanum) seed [escin – decreases capillary permeability],
pot marigold (Calendula officinalis) flower, ginseng (Panax ginseng) root [ginsenosides]
Raw materials containing steroid saponins: yam (e.g. Dioscorea zingiberensis) tuber, fenugreek
(Trigonella foenum-graecum) seed [diosgenin]
pelargonidin
cyanidin
delphinidin
malvidin
peonidin
petunidin
e.g. ginsenosides
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CARDIAC GLYCOSIDES
cardenolide type
bufadienolide type
e.g.
digoxigenin
e.g.
scillarenin
Glycone: 1-4 sugars at C-3
primary glycosides
secondary glycosides
e.g.:
lanatoside C (digoxigenin-digitoxose-digitoxose-acetylodigitoxose-glucose)
digoxin (digoxigenin-digitoxose-digitoxose-digitoxose)
Biological activity of cardiac glycosides:
increase the force of contraction of the heart muscle (positive inotropic effect)
decrease the rate of contractions (negative chronotropic effect)
increase cardiac output
indirect diuretic effect; reduction of swellings
indications: systolic heart failure, arrhythmia: atrial flutter, atrial fibrillation
Aglycone is responsible for the direction of activity.
Sugar moiety affects the solubility, absorption, strength and time of action,
ability to bind blood plasma proteins.
Strength of activity: aglycones < primary glycosides < secondary glycosides
Raw materials containing cardenolide glycosides: Grecian foxglove (Digitalis lanata) leaf [used
only for isolation of cardiac glycosides], lily of the valley (Convallaria majalis) herb,
spring adonis (Adonis vernalis) herb
Raw materials containing bufadienolide glycosides: sea squill (Drimia maritima) bulb
Aglycone:
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ANTHRAGLYCOSIDES
Aglycone: anthrone, dianthrone, anthranol or anthraquinone
Glycone: 1-3 sugars, mainly glucose and rhamnose
Type of glycoside bond: O- or C-
Biological activity of anthraglycosides:
laxative
reduce water absorption from the large intestine
irritate colon walls
stimulate peristalsis
accelerate colonic transfer
The most active compounds are dianthrones and anthrones.
Anthraglycosides are hydrolysed by colon microflora to aglycons and reduced to anthrones.
More sugar moieties in a glycoside and C-glycoside bond
stronger laxative activity.
cholagogue
enhancing gastric juice secretion
long-term use
irritation of gastrointestinal tract
vomiting, bloody diarrhoea
contraindications: pregnancy, lactation, acute intestinal inflammation, e.g. colitis ulcerosa
Raw materials containing anthraglycosides: alder buckthorn (Frangula alnus) bark,
senna (Senna alexandrina) leaf, rhubarb (Rheum palmatum) root, aloe (Aloë ferrox) leaf juice
Naphthodianthrones
anthraquinone
anthrone
anthranol
dianthrone
hypericin R=H
pseudohypericin R=OH
Biological activity of hypericin:
- photosensitising
- antidepressant
- anti-inflammatory
- antiviral (e.g. against HIV-1)
- anticancer
in St. John’s wort (Hypericum perforatum) herb
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COUMARINS
Coumarin is a product of hydrolysis of glycosides of coumaric acid (e.g. melilotoside) during
drying of raw material → specific smell
Hydroxycoumarins – occur in plants as free compounds or aglycones of glycosides (e.g. esculin=
esculetin glycoside).
Biological activity of coumarins:
UV-protecting, e.g. esculin, umbelliferone
sedative, e.g. coumarin
spasmolytic, e.g. coumarin
hypotensive, e.g. scopoletin
anticoagulant, e.g. dicoumarol, coumarin
cholagogue, e.g. fraxidin, isofraxidin
antioxidant
hepatotoxic, e.g. coumarin
Raw materials containing coumarins:
coumarin: yellow melilot (Melilotus officinalis) herb, sweet woodruff (Galium odoratum) herb,
Southern sweetgrass (Hierochloë australis) herb
hydroxycoumarins: chamomile (Matricaria chamomilla) flower head [umbelliferone],
common ash (Fraxinus excelsior) bark [isofraxidin], southernwood (Artemisia abrotanum) herb,
horse chestnut (Aesculus hippocastanum) bark [esculin],
raw materials obtained from plants from the family Apiaceae, e.g. lovage (Levisticum officinale)
root, garden angelica (Angelica archangelica) root
Biological activity of furanocoumarins:
photosensitising, e.g. psoralene, bergaptene, xanthotoxin (but not angelicin)
used for the treatment of vitiligo and psoriasis
spasmolytic, e.g. angelicin
vasorelaxant
blocking Ca
2+
channels in heart, e.g. imperatorin
cns depressant, e.g. angelicin
Raw materials containing furanocoumarins: rue (Ruta graveolens) herb, garden angelica (Angelica
archangelica) root and fruit, parsnip (Pastinaca sativa) fruit
hogweed (Heracleum sp.)
COOH
O
Glu
Coumarins
Furanocoumarins
COOH
OH
O
O
melilotoside
coumarinic acid
coumarin
O
O
O
O
O
O
psoralene-type
angelicin-type
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PHENOLIC GLYCOSIDES
Aglycone: phenol or its derivative
Phenolic acids
- occur in plants as free compounds, depsides (e.g. chlorogenic acid)
or aglycones of glycosides
- some of them are precursors of tannins
Biological activity of phenolic acids:
choleretic and cholagogue
antiviral
immunotropic
anti-inflammatory
detoxifying
antioxidant
Raw materials rich in phenolic acids:
knotweed (Polygonum aviculare) herb,
oregano (Origanum vulgare) herb,
lemon balm (Melissa officinalis) leaf,
purple coneflower (Echinacea purpurea) herb,
poplar (Populus nigra) buds
O
O
O
CH
3
O
Glu
OH
O
Glu
OH
O
Glu
arbutin – hydroquinone glucoside
bearberry (Arctostaphylos uva-ursi) leaf
lingonberry (Vaccinium vitis-idaea) leaf
Hydroquinone (product of hydrolysis of arbutin in urinary tract):
- disinfects urinary tract
- potent mutagenic activity
salicin – glucoside of salicylic alcohol (saligenin)
willow (Salix alba, S. purpurea) bark
poplar (Populus nigra) buds
Activity: antipyretic, anti-inflammatory
esp. in rheumatic disorders
O
Glu
HOH
2
C
leiocarposide
European goldenrod (Solidago virgaurea) herb
Activity: diuretic
O
H
O
H
CH
CH
COO
Glu
Glu
Rmn
O
CH
2
CH
2
OH
OH
echinacoside – phenylpropane derivative
narrow-leaf purple coneflower (Echinacea angustifolia) root
Activity: immunostimulant, antiviral
OH
OH
O
O
H
O
H
O
OH
O
OH
O
H
O
H
OH
O
O
OH
OH
salicylic acid
caffeic acid
chlorogenic acid
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IRIDOID GLYCOSIDES
Raw materials: eyebright (Euphrasia rostkoviana) herb,
wool mullein (Verbascum densiflorum) flower, ribwort plantain (Plantago lanceolata) leaf,
common plantain (Plantago major) leaf
harpagoside – in devil’s claw (Harpagophytum procumbens) root
– analgesic (in arthritic pains)
– anti-inflammatory
STEROLS
Occur in plants as free sterols (e.g. β-sitosterol, stigmasterol, campesterol), sterol glycosides or
sterol esters.
Biological activity of sterols:
lowering blood cholesterol level
antioxidant
anticoagulant
preventing prostatic hyperplasia
anti-inflammatory
preventing colon cancer
immunostimulatory
anti-ulcer
Raw materials with high sterol content:
stinging nettle (Urtica dioica) root, fireweed (Chamerion angustifolium) herb,
pumpkin (Cucurbita pepo) seed,
red stinkwood (Prunus africana) bark, saw palmetto (Serenoa repens) fruit
O
H
CH
3
CH
3
CH
3
CH
3
H
H
H
H
H
H
C
H
3
O
O
Glu
CH
2
OH
OH
aucubin (aucuboside)
- bacteriostatic
- anti-inflammatory
- hepatoprotective
β-sitosterol
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TANNINS
- large-molecule polyphenolic substances capable of binding proteins
hydrolysable tannins: gallotannins (esters of gallic acid),
ellagitannins (esters of ellagic acid)
condensed tannins (composed of numerous catechin molecules)
Biological activity of tannins:
astringent (protein coagulating)
wound healing
reduce bleeding from gastrointestinal tract
anti-inflammatory
anti-diarrhoea
antibacterial
antiviral
detoxifying (e.g. they bind alkaloids)
antioxidant
used for a long time in larger doses – decrease absorption of vitamins and minerals
Raw materials with high tannin content: oak (Quercus robur, Q. petraea) bark,
bistort/snakeweed (Bistorta officinalis) rhizome, tormentil (Potentilla erecta) rhizome,
common avens (Geum urbanum) herb and rhizome, great burnet (Sanguisorba officinalis) herb,
silverweed (Potentilla anserina) herb, bilberry (Vaccinium myrtillus) fruit,
willow (Salix alba, S. purpurea) bark, lingonberry (Vaccinium vitis-idaea) leaf,
sage (Salvia officinalis) leaf
BITTER COMPOUNDS
- bitter taste
- varied chemical structures, most often:
sesquiterpene lactones, e.g. absinthin in wormwood (Artemisia absinthium) herb
secoiridoids:
e.g. gentiopicroside – in yellow gentian (Gentiana lutea) root
amarogentin
sweroside
loganin
Activity:
increase the secretion of saliva and gastric juice
improve appetite and digestion
improve intestinal absorption
in bogbean (Menyanthes trifoliata) leaf
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ESSENTIAL OILS
obtained mainly by steam distillation of plant raw materials
in plants they occur in special cells or reservoirs:
exogenous:
- glandular trichomes:
• simple, e.g. capitate trichomes
• multicellular (e.g. asteraceous glandular trichomes – in the family Asteraceae,
peltate glandular trichomes – in the family Lamiaceae)
endogenous:
- essential oil cells
- secretory reservoirs
- secretory ducts (e.g. in caraway fruit, anise fruit, angelica root)
- resin canals (e.g. in pine needles)
physical traits of essential oils:
- usually liquid consistence
- usually colourless or yellowish; also brownish, blue or green
- readily volatile
- intensive smell
- insoluble in water
- usually of lower density in comparison with water
mixtures of volatile compounds of different chemical nature, mainly:
- terpenes (mono- and sesquiterpenes)
monoterpenes: e.g. menthol (peppermint essential oil), carvone (caraway essential oil),
thujone (wormwood e.o., tansy e.o.)
sesquiterpenes: e.g. α-bisabolol, chamazulene (chamomile e.o.)
- phenols and their derivatives
phenols: e.g. thymol (thyme e.o.), anethol (anise e.o., fennel e.o.)
- heterocyclic derivatives of aromatic compounds: phthalides (lovage e.o.)
- esters of organic acids
- coumarins
Biological activity of essential oils:
skin irritating, hyperemic (e.g. rosemary, pine, eucalyptus)
diuretic (e.g. juniper)
expectorant (e.g. anise, fennel, thyme, eucalyptus)
antiphlogistic (e.g. chamomile)
antiseptic (e.g. thyme, clove, marjoram)
choleretic, cholagogue (e.g. peppermint, pine)
anti-spasmodic, carminative (e.g. chamomile, caraway, fennel, dill, coriander, peppermint)
antineuralgic (e.g. pine, juniper)
sedative (e.g. valerian, lemon balm)
anthelmintic (e.g. wormwood, tansy, rosemary)
Essential oil-containing raw materials:
- obtained from plants from the family Lamiaceae: peppermint (Mentha x piperita) leaf,
lemon balm (Melissa officinalis) leaf, sage (Salvia officinalis) leaf,
rosemary (Rosmarinus officinalis) leaf, thyme (Thymus vulgaris) herb,
marjoram (Origanum majorana) herb, lavender (Lavandula angustifolia) flower
- obtained from plants from the family Apiaceae: caraway (Carum carvi) fruit,
fennel (Foeniculum vulgare) fruit, dill (Anethum graveolens) fruit,
coriander (Coriandrum sativum) fruit, anise (Pimpinella anisum) fruit,
garden angelica (Angelica archangelica) root, lovage (Levisticum officinale) root and leaf
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- obtained from plants from the family Asteraceae: chamomile (Matricaria chamomilla)
flower head, yarrow (Achillea millefolium) herb, wormwood (Artemisia absinthium) herb,
tansy (Tanacetum vulgare) herb
- obtained from other plants: hop (Humulus lupulus) strobile, pine (Pinus sylvestris) buds,
juniper (Juniperus communis) cone berry, calamus/sweet flag (Acorum calamus) rhizome
Some plants contain scentless, non-volatile precursors of volatile compounds. These plants also
contain specific enzymes catalysing the conversion of these precursors to volatile forms. The
precursors and the enzymes are stored in separate compartments of the cell. Releasing of volatile
compounds is only possible after plant injury (e.g. during chopping or crushing).
GLUCOSINOLATES – S-glycosides commonly occurring in the family Brassicaceae,
e.g. sinigrin – in black mustard (Brassica nigra) seed, horseradish (Armoracia rusticana) root
SULPHUR COMPOUNDS IN ALLIUM SP. (e.g. in garlic)
sinigrin
myrosinase
N
C
S
allyl isothiocyanate
H
2
O
highly volatile
irritates skin and mucous membranes
pungent taste
enhances gastric juice and bile secretion
non-volatile
non-volatile
volatile
burning taste, intensive smell
antibacterial, antifungal,
anti-aggregatory activity
other sulphur compounds
allicin
alliinase
alliin
x 2
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ALKALOIDS
True alkaloids
• derivatives of amino acids containing nitrogen in a heterocyclic ring
- tropane alkaloids
e.g.
atropine, scopolamine
Raw materials: downy thorn-apple (Datura inoxia) leaf,
Jimsonweed (Datura stramonium) leaf, deadly nightshade (Atropa belladonna) root
- isoquinoline alkaloids
e.g.
morphine, codeine – in opium poppy (Papaver somniferum)
papaverine – in opium poppy (Papaver somniferum)
chelidonine – in celandine (Chelidonium majus) root
- indole alkaloids
e.g.
ergometrine, ergotamine, ergotoxine – in ergot (Claviceps purpurea)
vinblastine, vincristine – in Catharanthus roseus leaf
- quinoline alkaloids
e.g.
quinine, quinidine – in Cinchona officinalis bark
- quinolizidine alkaloids
e.g.
sparteine – in Scotch broom (Sarothamnus scoparius) herb
- pyrrolizidine alkaloids
e.g. in borage (Borago officinalis), comfrey (Symphytum officinale),
coltsfoot (Tussilago farfara) → hepatotoxic, carcinogenic
- pyridine alkaloids
e.g. nicotine – in tobacco (Nicotiana tabacum)
Pseudoalkaloids
• nitrogen-containing compounds biogenetically not related to amino acids;
derivatives of terpenes, steroids, purines
e.g. purine alkaloids: caffeine, theobromine, theophylline
Protoalkaloids
• derivatives of amino acids,
but nitrogen in their molecules is not included in a heterocyclic ring
e.g. capsaicin – in red pepper (Capsicum annuum) fruit
ephedrine – in Chinese ephedra (Ephedra sinica)