1
OLIGOSACCHARIDES
Products of condensation of two-ten monosaccharides, connected by
glycosidic bond.
Glycosidic bond is formed:
• by hemi-acetal hydroxyl (at anomeric carbon of monosaccharide)
• and whichever hydroxyl of further monosaccharide (if formating
disaccharides),
• hydroxyl longer or shorter saccharide chain (if formating oligo- or
polysaccharides)
Glycosidic bond is cleaved:
• easily by hydrolysis (in acids)
• enzymatically (significant enzymatic specifity)
DISACCHARIDES
The way of formation of glycosidic bond enable to
divide disaccharides into two groups:
• Reducing
• Non-reducing
2
DISACCHARIDES
Reducing
The glycosidic bond enters
hemi-acetyl hydroxyl of one
sugar only. The other hemiacetyl-hydroxyl
is free,
disaccharide possesses
reducing power, can
mutarotate and can formate
glycosides. These
disaccharides are known as
„maltose type“
O
O
OH
OH
OH OH
O
OH OH
OH
OH
O
H
OH
OH
CH2OH
OH
O
OH
OH
OH
CH2OH
O
1
4
1 4
4-O--D-glukosyl-D-glucose
O--D-Glcp-(1---4)-D-Glcp
DISACCHARIDES
Non-reducing
The glycosidic bond enter hemiacetyl
hydroxyl groups of
both reacting
monosaccharides. These
sachcharides do not
mutarotate, do not make
osazones. Trehalose is found
in fungi and other nonphotosynthetising
organisms.
„Blood sugar of insects“
„Trehalose type“
O
OH
OH
OH
CH2
O
H
OH
OH
OH
CH2OH
O
HO1 1
O--D-Glcp-(1---1)--D-Glcp
3
DISACCHARIDES
The only non-reducing disaccharide of industrial importance is sucrose
(saccharose).
World production more than 150 millions tons, ¾ from sugar cane
SACCHAROSUM ČL 2009
Saccharum officinarum L. – sugar cane (Poaceae)
• perennial C4-plant (product of CO2 fixation is
malate or aspartate)
• stem (haulm) is solid with internodia
terminated with panicle of flowers
• Juice of crushed stems – removal of proteins,
filtration, and concentration, crystallization of
raw „brown“ sugar. The brown sugar is further
refined.
• Asia, South America and Caribbean islands are
main producers, cca 100 millions tons/year
O
OH
OH
OH
OH
O
OOH
OH
OH
OH
O
OH
OH
OH
CH2OH
O
OH
H
O
OH
CH2OH
CH2OH
O--D-Glcp-(1---2)--D-Fruf
SACCHAROSE
Beta vulgaris L. – sugar beet (Chenopodiaceae)
• biennial plant cultivated as annual, from the beginning of 19th century used as
raw material of production of sucrose.
• contains 16 – 17 % of sucrose, cca 77 % of water
• Tubers are sliced to sugar beet „cossettes“, extracted with hot water, the
obtained juice is purified. Concentration, crystallization (the residue is
molasses). Rafination.
• 1000 kg of sugar beet → 130 kg sucrose
Acer saccharophorum (A. saccharum) C. Koch – sugar maple (Aceraceae)
• three of eastern part of North American continent
• saccharose excreted from leaves and from rupture of bark (three courted by
bees)
Phoenix dactylifera L. – date palm (Palmae)
• Fruits are rich on sucrose
4
http://www.food-info.net/images/sugarcane2.jpg
http://www.recipetips.com/images/glossary/b/beets_sugar.jpg
5
http://wahyuinqatar.files.wordpress.com/2009/06/16062009692.jpg
Saccharose biosynthesis
O
OH
O
CH2OH
OH
OH
O
OH
OH
CH2OPO3H2
CH2OH O
OH
O
CH2OH
OH
OH
O
OH
OH
CH2OH
CH2OH
D-Fructose-6-phosphate
Phosphoglucose
isomerase
D-glucosa-6-phosphate
Phosphogluco
mutase
D-glucose-1-phfosphate
UDP pyrophos-
phorylase
UTP
PPi
UDP-glucose
UDP
Saccharose phosphate synthase
 1 2
Saccharose- 6F-phosphate
1
1
6
6
Saccharose
phosphatase
H2O Pi
 1 2
Saccharose
1
1
6
6
6
DISACCHARIDES
as degradation products of oligomers and polymers
Maltose
Degradation product of starch
Malt sugar
Reducing disaccharide
Celobiose
Degradation product of cellulose
O
H
OH
OH
CH2OH
OH
O
OH
OH
OH
CH2OH
O
1 4
4-O--D-glucopyranosyl-D-glucose
O
OH
OH
O
O
H
OH
OH
OH
CH2OH
CH2OH
OH
4-O--D-glucopyranosyl-D-glucose
1 4
DISACCHARIDES
reducing disaccharides as part of glycosides, especially flavonoids
• RUTINOSE O--L-Rhap-(1→2)-D-Glcp
• NEOHESPERIDOSE O--L-Rhap-(1→6)-D-Glcp
• MALTOSE O--D-Glcp-(1→4)-D-Glcp
• CELLOBIOSE O--D-Glcp-(1→4)-D-Glcp
• SOPHOROSE O--D-Glcp-(1→2)-D-Glcp
• LAMINARIBIOSE O--D-Glcp-(1→3)-D-Glcp
• GENTIOBIOSE O--D-Glcp-(1→6)-D-Glcp
• LACTOSE O--D-Galp-(1→4)-D-Glcp
• SCILLABIOSE O--D-Galp-(1→3)--L-Rhap
• SAMBUBIOSE O--D-Xylp-(1→2)-D-Glcp
• PRIMEVEROSE O--D-Xylp-(1→6)-D-Glcp
7
DISACCHARIDES
Lactose
The most important sugar in
mammalian mother milk (6 %).
Mother milk contains also cca 0,3
% of oligosaccharides.
O--D-Galp-(1→4)-D-Glcp
Isomaltose
Product of starch hydrolysis in place of
branching of linear chain
O
H
OH H
OH
CH2OH
OH
OO
H
OH
OH
OH
CH2OH
O
OH
OH
OH
CH2OH
O
O
H
OH
OH
OH
CH2
OH
O--D-Glcp-(1-6)-D-Glcp
HIGHER OLIGOSACCHARIDES
TRISACCHARIDES
UMBELLIFEROSE
-D-Galp-(1→2)--D-Glcp-(1→2)--D-Fruf
O
OH
OH
CH2OH
OH O
H
OH
CH2OH
OH
O
OHOH2C
OH
CH2OH
O
OH
isomelibiose
saccharose
8
HIGHER OLIGOSACCHARIDES
TRISACCHARIDES
RAFINOSE
-D-Galp-(1→6)--Glcp-(1→2)-
--D-Fruf
Part of molasses
Present is seeds of Fabaceae
plants → flatulence
O
OH
OH
CH2OH
OH
O
H
OH
OCH2
OH
OH
OHOH2C
OH
CH2OH
O
OH
melibiose
saccharose
RAMIFIED OLIGOSACCHARIDE
GYPSOSIDE A, O-glycoside (C-3), ester of (C-28) triterpenoid aglycon gypsogenine
Gypsophila paniculata L. – baby´s breath (Caryophyllaceae)
O
O
O
CHO
3
28 -L-Rha
-D-Xyl -D-Xyl
-D-Fuc -D-Xyl
-D-GlcA
-L-Ara
-D-Glc
-D-Gal
9
RAMIFIED OLIGOSACCHARIDE
Extremely effective adjuvant, QS-21A increasing effectiveness of antigen
administered to body to provoke immune response, allows to decrease dosage of
vaccine with higher effect
O
OH
OH
OH
OH
O
OH
OH
OH
O
Me
H
Me
H
Me
O
Me
Me
H Me OH
CO O R
HOOC
OH
O
O
CHO
O
OH Me
OH
O O
OH
O
OH
R1O Me
O
OH
O
R
O OH
O
Me
Me
O OH
O
Me
Me
O
OH
OH
OH
-D-GlcUA
-D-Xyl
-D-Gal
-D-Fuc
-D-Xyl
-L-Rha
-L-Ara
-D-Xyl-D-Api neboR1=
quillaic acid
10
POLYSACCHARIDES
HIGH-MOLECULAR, LINEAR OR RAMIFIED POLYCONDENSATES,
WIDESPREAD IN PLANTS, WHERE THEY POSSESS DIFFERENT
FUNCTION:
• SUPPORTING (cellulose)
• RESERVE (starch)
PHARMACEUTICALLY IMPORTANT POLYSACCHARIDES
• cellulose and its derivatives
• starches
• gums and mucilages
• pectins (polyuronides)
• polysaccharides from microorganisms and fungi
• Polysaccharides of animal origin, mucopolysaccharides
POLYSACCHARIDES – GLYCANS
HOMOGENIC
Composed from large number of the molecules of the same sugar unit
HETEROGENIC
Produced by condensation of molecules of different sugar types
• Hexoses
• Pentoses
• Anhydrohexoses
• Sugar ethers
• Sugar sulphates
• Aminosugars
LINEAR
RAMIFIED
11
TYPES OF POLYSACCHARIDES
POLYSACCHARIDES WITH REGULAR SEQUENCE (amylose, cellulose ….)
• β-(1→4), shape – very prolonged strip
• α-(1→4), polymer can be spiral-shaped (for example amylose)
• conformation is free, flexible, for example (1→6)
DISRUPTED SEQUENCE OF POLYSACCHARIDES
• areas with precise regularity alternate heterogeneous areas
• potential interaction „polymer – polymer“ enables the formation of gel
POLYSACCHARIDES COMPLETELY HETEROGENOUS
• interaction of „polymer – solvent“ can be found
ISOLATION AND STRUCTURAL ANALYSIS
ISOLATION
• water solvents
• Possibility of acid or salt addition
PURIFICATION
• Gel filtration
• Extraction with organic solvent
FRACTIONATION
• Precipitation techniques (change of pH)
• Chromatography (active char coal, ion exchange)
PURITY VALIDATION
• Optical rotary power
• Molecular weight
• Electrophoresis
12
STRUCTURAL ANALYSIS
Physical methods:
• spectrometry
• MS, NMR
Chemical methods
• partial hydrolysis
• derivatives formation
• controlled degradation
POLYSACCHARIDES OF MICROORGANISMS
AND FUNGI
Utilization of biotechnologies, increased number of production
organisms and products
DEXTRANS
• Leuconostoc, Lactobacillus, Streptococcus
• Polymers of glucose from α-D-glucopyranosyl units (bonds
predominantly 1-6, less often 1-3 and 1-2), high-molecular 40-50 × 106
• Synthesis with help of specific enzyme (exocellular, transfer of Glc
from saccharose)
• Adjustment by partial hydrolysis to 40000-75000 (acid hydrolysis,
sonication, bacteria)
13
XANTHANI GUMMI - XANTHAN GUM (ČL 2009)
• high-molecular anionic polysaccharide, in form of natrium, potassium or
calcium salt
• produced during the sugar fermentation (glucose or sucrose) with help
of microorganic species Xanthomonas campestris
• composed from main chain derived from β(1→4)- bonded D-glucose
units with trisaccharide secondary chains (at exchanging
anhydroglucose units) composed of glucuronic acid between two
mannose units. Majority of terminal units is substituted with pyruvic
acid and mannose neighboring the main chain can bee C-6 acetyled
• molecular weight approximately 1 × 106
• properties: white or yellowish loose powder; well dissolve-able in hot
and cold water (making highly viscous solution), viscosity does not
change with changing temperature
• insoluble in organic solvents; resistant to enzymes, rare
incompatibilities, tolerate up to 50 % of alcohol
• E number E415.
XANTHANI GUMMI - XANTHAN GUM (ČL 2009)
O
CH2OH
OH
O
CH2OH
OH
OH
O
O
O
O
OH
OH
OCH3
O
O
O
OH
OH
COOH
O
O
OH OH
O
O
n
CH3
COOH
R6
R4
R6
R4
GlcUAMan
Man6-Ac
-D-Glcp-(1--4)--D-Glcp-(1--4)...
pyruvát
14
XANTHANI GUMMI - XANTHAN GUM
…→)-β-D-Glcp-(1→4)- β-D-Glcp-(1→4)- β-D-Glcp- …
1→3
α-D-Manp-6-O-Ac
1→2
β-D-Glcp-A
β-D-Manp
4( )6
CH3-C-COOH
1→4
XANTHANI GUMMI - XANTHAN GUM (ČL 2009)
USAGE (E415)
Pharmacy: stabilizer of emulsions, adjuvant
Does not contain gluten, used in gluten-free bakery (makes the dough adhesive).
Coeliac disease – gluten intoleration (shorter protein cuts – gliadin in wheat,
secalin in rye, hordein in barley, avenin in oat)
Food industry: Stabilisators, thickener of products based on water (milk products,
dressings, dips, sauces, instant soups, sirups), ice-creams (prevent formation of ice
crystals); Activia, Pribináček, Tartar sauce, Tisíc ostrovů, Křemílek, Thai Kari,
Hermelin salad and others.
Cosmetics: creams, tooth pasts (stabilizer)
15
POLYSACCHARIDES OF FUNGI
Lentinan (Lentinus edodes – SHIITAKE)
Homogenous polyglucan
• β-(1-3) bonds, rarely 1-6 bonds
• Immune-modulating effects
• Antitumor activity
• human clinical studies showed higher survival rate, higher quality of
life, and lower recurrence of cancer
(1) prevention of onset of cancer by oral consumption of mushrooms or their preparations
(2) direct inhibition of growth of various types of cancer cells
(3) immuno-stimulating activity against cancers in combination with chemotherapy
(4) preventive effect on spreading or migration of cancer cells in the body
Basidiomycetes:
Pachymaran
Schizophyllan
Krestin (Coriolus versicolor)
16
POLYSACCHARIDES OF ALGAE
• Phaeophyta
Alginic acids (alginate), fucans
• Rhodophyta
Sulphated galactans (agar, carrageen)
• Chlorophyta
Complex polysaccharides, often sulphated
POLYSACCHARIDES OF ALGAE
Phaeophyceae
chlorophyll A and C, β-carotene, fucoxanthine (xanthophylls), alginates,
15–40 % of drug dry weight
Laminaria spp.
Brown alga, seacoast of France and England
Industrial processing, colloid chemistry
Macrocystis pyrifera
Californian kelp, giant algae of Pacific
Fucus serratus, F. vesiculosus
Seacoast of England
17
Laminaria digitata Fucus vesiculosus Macrocystis pyrifera
http://diver.net/californiadiveboats.com/OceanOdyssey/2008.02.23/
http://www.dermaxime.com/seaweed-extracts.htm
Alginic acid, alginates
Mixture of uronic acids, 19-25 % of carboxyls
Linear polymer of D-mannuronic acid-β(1→4)-L-guluronic acid
Blocks of same acids alternate in linear chain
In form of salt (Na, Mg, Ca)
Properties
• Salts with Na and Mg → colloid solution
• Salts with Ca → elastic gel
Usage
• Antacids in combination with NaHCO3 a Al(OH)3
• Haemostatic - stomatology, superficial wounds
• Pharmaceutical technology
• Food industry E400-405
O
HOOC
O
OH
OH
O
O
OHHOOC
OH O
O
HOOC
O
OH
OH
O
O
O
COOH
OH
OH
block of mannuronic acids
block of guluronic acid
18
CARRAGEENAN – Karagen, Irish moss syn. Alga carrageen,
Chondrus crispus and Gigartina mamillosa (Gigartinaceae)
Polymers of D-galactose, anionic character,
sulphated, molecular weight 105-106
• Bonds 1→3 (A unit) and 1→4 (B unit)
• Sulphatation at positions 2 and 6 or 2 and 4
• Different structural subtypes
• Properties
• Based on subtype
• Usually soluble in hot water
• Some of them produce gel
• Usage:
• Technology
• Laxative
• Cosmetics
• Additives of food
O
OH
OH
CH2OH
OH
OH
D-galactose
6
2
4
O
OH
OHOH
O
anhydro-D-galactose
CARRAGEENAN
types
A unit B unit Type
D-galactose-4-sulphate D-galactose-6-sulphate μ
D-galactose-2,6-disulphate υ
3,6-anhydro-D-galactose κ
3,6-anhydro-D-galactose-2-sulphate ι
D-galactose-2-sulphate D-galactose-2-sulphate ζ
D-galactose-2,6-disulphate λ
3,6-anhydro-D-galactose-2-sulphate θ
19
Chondrus crispus – Irish moss
• Karageenans
• Chlorophyll A and D
• Fycoerythrin
• Starch typical for red
algae
POLYSACCHARIDES OF ALGAE
Agar
• Different Rhodophyceae (red algae)
• Mostly Gelidium
• Chemical properties
• Complex galactan
• Agarose and agaropectin
• Agarose
• Linear polymer
• (AB)n 1→3 and 1→4 bond
• A – partially methylated D-galactose
• B – L-galactose (3,6 anhydroform)
• Sulphated poorly
• Agaropectin
• ramified
• Properties:
• Soluble in hot water
• Jellifying around 30-35°C, around 80°C liquefying
• Agarose formates double helix, formates 3D structure by bounding water units
• It is not metabolized, it is not toxic
• Usage
• Laxative, nutritive medium for microbiology, chromatography, electrophoresis, E406
O
OH
O
CH2OH
OH
O
O
OH
CH2OH
OH
O
O
OH
OHO
OH
CH3
HOOC
A B
20
http://www2.naris.go.kr/v2/naris_search/search_result_detail.jsp?inst_id=1165083
Gelidium amansii
21
POLYSACCHARIDES OF HIGHER PLANTS
• Starches
• Cellulose
• Polyfructosans
• Dietary fibre
AMYLA (starches)
Macromolecules formed by glucose units
• Amylose (20-30 %)
• 250-300 Glc residues; (1→4)-α-D-glykosidic bond
• Basic building block is maltose
• Amylopectin (70 %)
• 1000 Glc residues; (1→4)-α-D-glycosidic bond and
(1→6)-α-D-glycosidic bond – branching cca after
25 units of Glc
22
Physico-chemical properties of starch
Insoluble in cold water and organic solvents
Swelling in cold water
Soluble in hot water → formation of wheatpaste – colloid
starch solution
According to the origin grains of different shape, size and
structure
Careful hydrolysis gives arise to dextrins
MODIFIED STARCHES
Physical modification
• Boiling and dehydration
Chemical modification
• Oxidation
• Esterification
• Cationisation or anionisation
• Etherification
• Hydrogenation
Controlled depolymerisation
• Partial hydrolysis
• Enzymatically
• Debranching enzymes
23
STARCH UTILIZATION
• Pharmaceutical additive
• Reagent for production of dextrin
• Textile industry
• Paper mills
NATURAL SOURCES OF STARCH
Oryza sativa (Poaceae), rise – Oryzae amylum
Triticum aestivum (Poaceae), wheat – Tritici amylum
Solanum tuberosum (Solanaceae), potatoe – Solani amylum
Zea mays (Poaceae), corn – Maydis amylum
24
CELLULOSUM – CELLULOSE
High-molecular linear polymer of D-Glc units bonded β-(1→4)
• Basic building block – cellobiose
• Native cellulose – degree of polymeration up to 15000
O
CH2OH
OH
OH
OH
O
OH
CH2OH
OH
O
O
OH
CH2OH
OH
O
CH2OH
OH
OH
O
O O
n
O
O
O
O
O
C
H2
O
O
H
H
H
O
OH
C
H2
O
H
O H
O
OH
C
H2
O
H
O
O H

11
4
4
4


14 1
Primary structure of cellulose
Linear cellulose chain stabilized by hydrogen bridges
CELLULOSUM – CELLULOSE
Diagram of micelle structure of cellulose
25
CELLULOSUM – CELLULOSE
CELLULOSUM
Almost pure cellulose
• Cotton wool fibers – trichomes from seeds of plants from Gossypium
species
Technical cellulose
• wood of conifers
• Purification from lignin and admixtures
Acetobacter xylinum
26
Lana gossypii depurata – bandage cotton wool purified from
cotton seeds
Gossypium spp. – cotton plant (Bombacaceae)
Gossypium spp.
• Asian variety
G. arboreum and G. herbaceum
• American variety
G. hirsutum and G. barbadense
Uni-cellular fibers
• 15-40 mm long
• 12-25 microns in diameter
• During ripening their distortion – textile quality
Processing
• Seeds separated mechanically
• Sorting according to the quality
27
Cellulosum ligni – bandage cellulose
Bleached cellulose from wood of Coniferae trees
Delignification in acid or under neutral conditions
Possibility of esterification
• Nitrate, acetate (different utilization)
• Soluble in water
• Solubility depends on degree of esterification DS 0-3
FURTHER PLANT FIBERS
Kapok – Ceidra pentandra (Malvaceae)
Flax fibers – Linum usitatissimum (Linaceae)
Hemp fiber – Cannabis sativa (Cannabaceae)
Jute – Corchorus capsularis (Tiliaceae)
28
DEXTRIN
Mixture of polysaccharides
Produced by mild hydrolysis of starches
• Heating
• Mineral acids
INULINUM - INULIN
Plant polyfructosan (furanoid form)
Bond β-(2→1) between D-fructose units
Less than 100 units of Fru
Well soluble in water
Occurrence – storage organs of Asteraceae plants and Poaceae plants
• Inula helenium
• Cichorium intybus
• Helianthus tuberosus
29
DIETARY FIBERS
• Dietary, chemical, physiological definitions
• Plant (vegetables) residues of non-digestible by
enzymes of GIT of human
• Macromolecules of cell wall and intracellular
polysaccharides
• Lignin
• Polysaccharides of different type than α-glucans
• cellulose
• pectins (glycano-galactans)
• Hemicelluloses
• galactomannans, heteroxylans, pentosans
• Glycoproteins
• Sources: fruits, vegetables, dried fruits, brans
DIETARY FIBERS
• Physiologic effects:
• Gastro-intestinal tract
• Increase of faeces volume (insoluble fraction)
• Affection of food passage through guts (insoluble
fraction)
• Effect of intestinal microflora
• Possible prevention of creation of colorectal carcinoma
• Affection of metabolic activity
• Interaction with intake of mineral compounds
• Level of blood cholesterol
• Level of blood sugar
30
GUMS AND MUCILAGES
Under term gums and mucilages can be found:
• Macromolecules of polysaccharides
• More or less soluble in water, usually format colloid solutions or gels
Today under naming „plant hydrocolloids“
Plant hydrocolloids are of interest in health care and industry.
Mucilages – protectives of mucose layers, expectorants/antitussics, laxatives
Gums – laxatives, anobesics, emulgators, stabilizers
MUCILAGES
Mucilages – normal content compounds pre-existing in
specialized histological formations (cells or tubules),
which are generally found in external covers of seeds.
Widely distributed, mostly in Malvales (acidic mucilages)
and Fabales (neutral mucilages of endosperm)
Swelling in water – active role in seed germination.
31
MUCILAGES
Mucilages – high-molecular polysaccharides
• strongly swelling in water (micellar solubility)
• dissolving into viscose colloid hydrophilic solutions
• Insoluble in ethanol and organic solvents
Hydrolysis
• hexoses and pentoses (mostly galactose and arabinose)
• sugar derivatives (anhydrides, uronic acids, esters with
sulphuric acid)
DRUGS CONTAINING MUCILAGES
• Althaeae radix – marshmellow root (ČL 2009)
• Althaeae folium – marshmallow leaf (ČL 2009)
• Farfarae folium – coltsfoot leaf
• Foenugraeci semen – fenugreek sead
• Lichen islandicus – island lichen (ČL 2009)
• Malvae sylvestris folium – mallow foilum
• Malvae sylvestris flos – mallow flower (ČL 2009)
• Plantaginis folium – plantain leaf
• Plantaginis ovatae semen – oval plantain seed (ČL2009)
• Plantaginis ovatae testa – testa of oval plantain (ČL 2009)
32
Cyamopsidis seminis pulvis (ČL 2009)
Cyamopsis tetragonolobus – Guar (Fabaceae)
Annual plant planted in USA, India, Pakistan
Commercial product is grinded endosperm (not exudate)
White powder, with water formats a mucilage of different viscosity, insoluble in
EtOH.
Content compounds: polysaccharides D-galacto-D-mannane (1→4)
Usage:
• hypercholesterolemia (prevention of cardiovascular diseases); lowers the level
of serum cholesterol and LDL without affection of other lipoproteins and
triglycerides;
• DM2; lowering of hyperglycaemia and post-prandial insulinemia (after food
intake)
• In combination with montmorillonite – symptomatic treatment of colonopathy
with constipation
Cyamopsidis seminis pulvis (ČL 2009)
Cyamopsis tetragonolobus – Guar (Fabaceae)
33
MANNOSE DERIVED MUCILAGES (NEUTRAL
MUCILAGES)
Rarely pure mannan
• Glucomannans
20-50 % of D-mannose replaced by D-glucose, β-(1→4)
Amorphophallus konjak
• Galactomannans
Part of D-mannose replaced by D-galactose
Ceratonia siliqua (Caesalpiniaceae), Annonaceae, Palmae
• Galactoglucomannans
Cercis siliquastrum Caesalpiniaceae
CERATONIAE SEMEN; KARRUBIN; LOCUST BEAN
GUM
Ceratonia siliqua (Caesalpiniaceae); Karob tree
Subtropic, evergreen, dioecious caulifloric woody plant. Pods ripen in following
year. Seeds are exceptional with regular weight, from ancient times weight
for measurement of amount of gold and gems: from Greec kerátion→carat =
200 mg
Content compounds:
galactomannan karrubin (up to 80 % of endosperm); flavones, oils with
linolenic acid; β-sitosterol
Usage:
• dietary fibers lowers the level of cholesterol, triglycerides, and blood glucose
• retains water in intestinal lumen
• roasted seeds → substitution of coffee, for production of chocolate for allergic
people and for dogs
• E410 – thickener, stabilizer of emulsions
34
Ceratonia siliqua (Caesalpiniaceae)
Karrubin – galaktomannan
O
OH
O
OH
OH
O
O
O
OH
OH
OH
O
O
OH
OH
OH
O
OH
OH
O
O
OH
OH
O
OH
OH
Gal
Man
Man Man Man
1
4
1
4 1
4 1
4
1
6





35
MANNOSE DERIVED MUCILAGES (NEUTRAL
MUCILAGES)
Trigonella foenum graecum
Fabaceae
Composition
• mucilages - galactomannans
• saponins
• essential oil – sesquiterpens
• lipids, proteins
• flavonoids
• cellulose
Usage
• compress, kataplasmata
• lowering of blood
cholesterol
• adjuvant therapy of DM2
ACID HETROGENOUS POLYSACHARIDES
(ACIDIC MUCILAGES)
Mucilages of Plantaginaceae
• Psyllium
Planatago afra (syn. P. psyllium)
P. indica (syn. P. arenaria
• Mediterranian
• Ispaghula
Plantago ovata (syn. P. ispaghula)
• India
Composition
• heteroxylan (D-xylose (70 %), Larabinose
(10 %), D-galaktose, α-D-
galakturonyl-(1→4)-L-xylose)
Usage
• mechanical laxative
• lowering of blood glucose
• lowering of LDL and total
cholesterol
• Irritable colon syndrom
36
ACIDIC HETEROGENOUS POLYSACCHARIDES
Mucilages of Malvaceae
• Malva silvestris
• Althaea officinalis
Strongly ramified structure
• Similar to pectins
• D-galactose, L-rhamnose, D-glucuronic
acid, D-galacturonic acid
Usage
• Symptomatic treatment of constipation
• Symptomatic treatment of cough
• Protective at GIT
Lini semen
Linum usitatissimum (Linaceae)
Containing:
• Oil, proteins
• Ramified mucilage: D-xylose, D-glucose,
L-arabinose, D-galactose
• Lignans
Usage
• Laxative
• Mucose layer protective
• Compresses
http://caliban.mpiz-koeln.mpg.de/~stueber/thome/band3/tafel_001.html
37
GUMS
Gums - clovatins
Common occurrence mainly at Mimosaceae, Rosaceae, Rutaceae, Burseraceae
Characteristics:
Optically active compounds, molecular weight 2 × 104 – 2 × 106; complex molecules, always
heterogeneous and ramified, containing uronic acids together with galactose, arabinose and xylose.
Often partially methylated or acetylated. Carboxylic groups can occurre in form of salt.
Pathologic products – flowing from plants after wounding (with exception of Tragacantha).
Formation:
transformation of other polysaccharides (probably also starches)
Characteristics
• amorphous optically active compounds
• soluble in water to format colloid hydrophilic solution, weakly acidic reaction in EtOH
• in organic solvents insoluble
• water solutions tends to glue
CLASSIFICATION OF GUMS
according to the structure and distribution in plant kingdom
A: Gums from Acacia plants (Gummi arabicum) contains enzymes
• main chain composed of 1→3 galactan substituted with L-arabinose
• ramification by L-rhamnose, D-xylose, D-glucuronic acid
• compatible with majority of hydrocolloids and majority of alkaloids
• incompatibility with gelatin, phenols (thymol, eugenol, morphine)
• stabilizers of suspensions, emulgator, with proteins formats coacervates
B: Gums similar to pectin, Karaya gum, Sterculia gum
• Sterculia urens and S. tomentosa
• 1→4 D-galacturonic acid
• branching with L-arabinose, D-glucuronic acid, D-galacturonic acids.
• non-toxic, non-metabolizing, non degraded
• laxative, anobesic, triggers the „feeling of saturation“ (contraindication is
stenose pylori), adhesive properties utilizable for fixation of tooth
prosthetics
• Utilization in pharmaceutical technology, food industry, cosmetics
38
CLASSIFICATION OF GUMS
according to the structure and distribution in plant kingdom
C:
• Uncommon 1→4 bonded xylans
• Often substitution with monosaccharides (L-Ara, D-Gal, D-GlcUA)
D:
• Main chain formed by repetition of (1→4 and 1→2) D-GlcUA and D-
Man
• C3-OH of majority of D-Man substituted with further sugars
• India, Sri Lanka
• Formation of emulsions, stabilizer
• Ghatti gum (Anogeissus latifolia, Combretaceae)
Acaciae gummi – Gummi arabicum (ČL 2009)
Acaciae gummi dispersione desiccatum – Arabic gum dried
by dispersion (ČL 2009)
Acacia senegal – gum arabic tree (Mimosaceae). African trees (Sudan).
On the air hardened clovatine flowing spontaneously or after cutting of
branches and stem, flowing gum desiccates into yellowish or jantar oval
pieces friable, opaque, without odor and taste.
Slowly soluble in doubled amount of water. Obtained liquid is dense, yellowish,
showing acidic reaction. Insoluble in ethanol.
Fresh gum is formed from:
• arabin – arabinic acid (salts of Ca, K, Mg), 1→3 galactan, side sugars are: LAra,
L-Rha, D-Gal, D-GlcUA.
• enzymes – incompatible with glycosides, therefore Acaciae gummi
desenzymatum is prepared
Utilization: stabilizer of suspensions, emulgator, adhesive. Production of
colorants, glues.
39
Acacia senegal – Arabic gum tree (Mimosaceae)
-β-D-Galp-(1→3) -β-D-Galp-(1→3)-β-D-Galp-(1→3)-β-D-Galp-(1→3)-)-β-D-Galp-(1→3)-
G
G
G
G
G
G
A
U
A
U
A
G
U
A
U
GA
G
G
G
G
G
G
A
U
A
U
GG
G
40
TRAGACANTHA – TRAGANT
Astragalus gummifer (Fabaceae)
Trees of Western Asia.
Obtained after cutting of branches and stems, flowing gums is without odor,
taste. Consistsof thin strips (30 × 10 × 1 mm) or their segments.
Fresh gum is formed from:
• tragacanthin (arabinogalactan, neutral, soluble in water and water/alcoholic
solvents)
• bassorin (partially methylated glycanogalacturonan, acidic)
Utilization: stabilizer of suspensions; bifunctional emulgator (increases viscosity
of water fraction and lowers superficial tension at interface O/W emulsions),
E413
Astragalus gummifer (Fabaceae)
41
Gums similar to pectin
Karaya gum, Sterculia gum
Sterculia urens a S. tomentosa
• 1→4 D-galacturonic acid with L-rhamnose
• branching with D-glucuronic acid, D-galaktose
• Non-toxic, non-metabolizing, non-degraded
• laxative, anobesic, triggers the „feeling of
saturation“ (contraindication at stenose pylori)
adhesive properties utilizable for fixation of
dental prosthetics
• Usage in pharmaceutical technology, food
industry, cosmetics
http://farm1.static.flickr.com/158/423923943_57dfa989e3.jpg
→2-α-L-Rhap-(1→4)-α-D-GalA-(1→2)-α-L-Rhap-(1→4)-α-D-GalA-1→
β-D-Galp
4
1
4
β-D-GlcA
3
1
β-D-Galp
2
1