Glycoside

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"Bioside" redirects here. For the poisonous substance or microorganism, see
Biocide.

Salicin, a glycoside related to aspirin

Chemical structure of oleandrin, a cardiac glycoside

In chemistry, a glycoside /ˈɡlaɪkəsaɪd/ is a molecule in which a sugar is bound to
another functional group via a glycosidic bond. Glycosides play numerous important
roles in living organisms. Many plants store chemicals in the form of inactive
glycosides. These can be activated by enzyme hydrolysis,[1] which causes the sugar
part to be broken off, making the chemical available for use. Many such plant
glycosides are used as medications. Several species of Heliconius butterfly are
capable of incorporating these plant compounds as a form of chemical defense
against predators.[2] In animals and humans, poisons are often bound to sugar
molecules as part of their elimination from the body.

In formal terms, a glycoside is any molecule in which a sugar group is bonded

through its anomeric carbon to another group via a glycosidic bond. Glycosides can
be linked by an O- (an O-glycoside), N- (a glycosylamine), S-(a thioglycoside), or
C- (a C-glycoside) glycosidic bond. According to the IUPAC, the name "C-glycoside"
is a misnomer; the preferred term is "C-glycosyl compound".[3] The given definition
is the one used by IUPAC, which recommends the Haworth projection to correctly
assign stereochemical configurations.[4]

Many authors require in addition that the sugar be bonded to a non-sugar for the
molecule to qualify as a glycoside, thus excluding polysaccharides. The sugar group
is then known as the glycone and the non-sugar group as the aglycone or genin part
of the glycoside. The glycone can consist of a single sugar group (monosaccharide),
two sugar groups (disaccharide), or several sugar groups (oligosaccharide).

The first glycoside ever identified was amygdalin, by the French chemists Pierre
Robiquet and Antoine Boutron-Charlard, in 1830.[5]

Contents
1 Related compounds
2 Chemistry
3 Classification
3.1 By glycone/presence of sugar
3.2 By type of glycosidic bond
3.3 By aglycone
3.3.1 Alcoholic glycosides
3.3.2 Anthraquinone glycosides
3.3.3 Coumarin glycosides
3.3.4 Chromone glycosides
3.3.5 Cyanogenic glycosides
3.3.6 Flavonoid glycosides
3.3.7 Phenolic glycosides
3.3.8 Saponins
3.3.9 Steroidal glycosides or cardiac glycosides
3.3.10 Steviol glycosides
3.3.11 Iridoid glycosides
3.3.12 Thioglycosides
4 See also
5 References
6 External links
Related compounds
Molecules containing an N-glycosidic bond are known as glycosylamines and are not
discussed in this article. (Many authors in biochemistry call these compounds N-
glycosides and group them with the glycosides; this is considered a misnomer, and
discouraged by IUPAC.) Glycosylamines and glycosides are grouped together as
glycoconjugates; other glycoconjugates include glycoproteins, glycopeptides,
peptidoglycans, glycolipids, and lipopolysaccharides.[citation needed]

Chemistry
Much of the chemistry of glycosides is explained in the article on glycosidic
bonds. For example, the glycone and aglycone portions can be chemically separated
by hydrolysis in the presence of acid and can be hydrolyzed by alkali. There are
also numerous enzymes that can form and break glycosidic bonds. The most important
cleavage enzymes are the glycoside hydrolases, and the most important synthetic
enzymes in nature are glycosyltransferases. Genetically altered enzymes termed
glycosynthases have been developed that can form glycosidic bonds in excellent
yield.[citation needed]

There are many ways to chemically synthesize glycosidic bonds. Fischer

glycosidation refers to the synthesis of glycosides by the reaction of unprotected
monosaccharides with alcohols (usually as solvent) in the presence of a strong acid
catalyst. The Koenigs-Knorr reaction is the condensation of glycosyl halides and
alcohols in the presence of metal salts such as silver carbonate or mercuric oxide.
[citation needed]

Classification

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Glycosides can be classified by the glycone, by the type of glycosidic bond, and by
the aglycone.

By glycone/presence of sugar
If the glycone group of a glycoside is glucose, then the molecule is a glucoside;
if it is fructose, then the molecule is a fructoside; if it is glucuronic acid,
then the molecule is a glucuronide; etc. In the body, toxic substances are often
bonded to glucuronic acid to increase their water solubility; the resulting
glucuronides are then excreted. Compounds can also be generally defined based on
the class of glycone; for example, biosides are glycosides with a disaccharide
(biose) glycone.

By type of glycosidic bond

Depending on whether the glycosidic bond lies "below" or "above" the plane of the
cyclic sugar molecule, glycosides are classified as α-glycosides or β-glycosides.
Some enzymes such as α-amylase can only hydrolyze α-linkages; others, such as
emulsin, can only affect β-linkages.

There are four type of linkages present between glycone and aglycone:

C-linkage/glycosidic bond, "nonhydrolysable by acids or enzymes"

O-linkage/glycosidic bond
N-linkage/glycosidic bond
S-linkage/glycosidic bond
By aglycone
Glycosides are also classified according to the chemical nature of the aglycone.
For purposes of biochemistry and pharmacology, this is the most useful
classification.
Alcoholic glycosides
An example of an alcoholic glycoside is salicin, which is found in the genus Salix.
Salicin is converted in the body into salicylic acid, which is closely related to
aspirin and has analgesic, antipyretic, and antiinflammatory effects.

Anthraquinone glycosides
These glycosides contain an aglycone group that is a derivative of anthraquinone.
They have a laxative effect. They are mainly found in dicot plants except the
family Liliaceae which are monocots. They are present in senna, rhubarb and Aloe
species. Anthron and anthranol are reduced forms of anthraquinone.

Coumarin glycosides
Here, the aglycone is coumarin or a derivative. An example is apterin which is
reported to dilate the coronary arteries as well as block calcium channels. Other
coumarin glycosides are obtained from dried leaves of Psoralea corylifolia.

Chromone glycosides
In this case, the aglycone is called benzo-gamma-pyrone.

Cyanogenic glycosides

Amygdalin
In this case, the aglycone contains a cyanohydrin group. Plants that make
cyanogenic glycosides store them in the vacuole, but, if the plant is attacked,
they are released and become activated by enzymes in the cytoplasm. These remove
the sugar part of the molecule, allowing the cyanohydrin structure to collapse and
release toxic hydrogen cyanide. Storing them in inactive forms in the vacuole
prevents them from damaging the plant under normal conditions.[6]

Along with playing a role in deterring herbivores, in some plants they control
germination, bud formation, carbon and nitrogen transport, and possibly act as
antioxidants.[6] The production of cyanogenic glycosides is an evolutionarily
conserved function, appearing in species as old as ferns and as recent as
angiosperms.[6] These compounds are made by around 3,000 species; in screens they
are found in about 11% of cultivated plants but only 5% of plants overall—humans
seem to have selected for them.[6]

Examples include amygdalin and prunasin which are made by the bitter almond tree;
other species that produce cyanogenic glycosides are sorghum (from which dhurrin,
the first cyanogenic glycoside to be identified, was first isolated), barley, flax,
white clover, and cassava, which produces linamarin and lotaustralin.[6]

Amygdalin and a synthetic derivative, laetrile, were investigated as potential

drugs to treat cancer and were heavily promoted as alternative medicine; they are
ineffective and dangerous.[7]

Some butterfly species, such as the Dryas iulia and Parnassius smintheus, have
evolved to use the cyanogenic glycosides found in their host plants as a form of
protection against predators through their unpalatability.[8][9]

Flavonoid glycosides
Here, the aglycone is a flavonoid. Examples of this large group of glycosides
include:

Hesperidin (aglycone: hesperetin, glycone: rutinose)

Naringin (aglycone: naringenin, glycone: rutinose)
Rutin (aglycone: quercetin, glycone: rutinose)
Quercitrin (aglycone: quercetin, glycone: rhamnose)
Among the important effects of flavonoids are their antioxidant effect. They are
also known to decrease capillary fragility.

Phenolic glycosides
Here, the aglycone is a simple phenolic structure. An example is arbutin found in
the Common Bearberry Arctostaphylos uva-ursi. It has a urinary antiseptic effect.

Saponins
Main article: Saponin
These compounds give a permanent froth when shaken with water. They also cause
hemolysis of red blood cells. Saponin glycosides are found in liquorice. Their
medicinal value is due to their expectorant, corticoid and anti-inflammatory
effects. Steroid saponins are important starting material for the production of
semi-synthetic glucocorticoids and other steroid hormones such as progesterone; for
example in Dioscorea wild yam the sapogenin diosgenin, in the form of its glycoside
dioscin. The ginsenosides are triterpene glycosides and ginseng saponins from Panax
Ginseng C. A. Meyer, (Chinese ginseng) and Panax quinquefolius (American ginseng).
In general, the use of the term saponin in organic chemistry is discouraged,
because many plant constituents can produce foam, and many triterpene-glycosides
are amphipolar under certain conditions, acting as a surfactant. More modern uses
of saponins in biotechnology are as adjuvants in vaccines: Quil A and its
derivative QS-21, isolated from the bark of Quillaja saponaria Molina, to stimulate
both the Th1 immune response and the production of cytotoxic T-lymphocytes (CTLs)
against exogenous antigens make them ideal for use in subunit vaccines and vaccines
directed against intracellular pathogens as well as for therapeutic cancer vaccines
but with the aforementioned side-effect of hemolysis.[10] Saponins are also natural
ruminal antiprotozoal agents that are potential to improve ruminal microbial
fermentation reducing ammonia concentrations and methane production in ruminant
animals.[11]

Steroidal glycosides or cardiac glycosides

Here the aglycone part is a steroidal nucleus. These glycosides are found in the
plant genera Digitalis, Scilla, and Strophanthus. They are used in the treatment of
heart diseases, e.g., congestive heart failure (historically as now recognised does
not improve survivability; other agents are now preferred[citation needed]) and
arrhythmia.

Steviol glycosides
Main article: Steviol glycoside
These sweet glycosides found in the stevia plant Stevia rebaudiana Bertoni have 40-
300 times the sweetness of sucrose. The two primary glycosides, stevioside and
rebaudioside A, are used as natural sweeteners in many countries. These glycosides
have steviol as the aglycone part. Glucose or rhamnose-glucose combinations are
bound to the ends of the aglycone to form the different compounds.

Iridoid glycosides
These contain an iridoid group; e.g. aucubin, geniposidic acid, theviridoside,
loganin, catalpol.

Thioglycosides
As the name implies (q.v. thio-), these compounds contain sulfur. Examples include
sinigrin, found in black mustard, and sinalbin, found in white mustard.

See also