OLIGOSACCHARIDES
Products of condensation of two-ten monosaccharides, connected by
glycosidic bond.
Glycosidic bodn is fromed:
• 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
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
CH2
OH
OH
O
OH
OH
OH
CH2
OH
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
CH2
OH
O
HO1 1
O--D-Glcp-(1---1)--D-Glcp
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
CH2
OH
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
http://www.food-info.net/images/sugarcane2.jpg
http://www.recipetips.com/images/glossary/b/beets_sugar.jpg
http://wahyuinqatar.files.wordpress.com/2009/06/16062009692.jpg
Saccharose biosynthesis
O
OH
O
CH2
OH
OH
OH
O
OH
OH
CH2
OPO3
H2
CH2
OH O
OH
O
CH2
OH
OH
OH
O
OH
OH
CH2
OH
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
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
CH2
OH
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
CH2
OH
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
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
CH2
OH
O
OH
OH
OH
CH2
OH
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
CH2
OH
OH
O
OHOH2C
OH
CH2OH
O
OH
isomelibiose
saccharose
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
CH2
OH
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