Sugars
Sugars
Sugars
Carbohydrates
Carbohydrates:
Monosaccharides
polysaccharides
Stereochemistry
Nomenclature
EFEKAT AHIRALNIH MOLEKULA propanal-3-ola NA RAVAN POLARIZOVANE
SVETLOSTI achiral molecule
chiral molecule
EFEKAT HIRALNIH MOLEKULA (jednog enantiomera)
Polarimeter should not be confused with refractometer.
Note:
Aldehyde is C-1
Penultimate is
second to the
last carbon,
determining D
or L
configuration
Natural sugars
are D
CHO
H OH
CHO
H OH
HO H
HO H
2D formula
odgovara vr. 3D
H OH Fisher formula (2D)
H OH H OH
CH2 OH
H OH
CH 2OH
H
O
HO
H OH
H
OH H
OH H
H
OH H
O
HO
H OH
H
OH H
OH H
H
H OH
CHO
H
CHOH
O O
O OH
CHOH
C H C H
CHOH
CHOH
CH 2OH
otopen
vor enichain
ni z otopen
vor eni chain
ni z pr st enast ihemiacetal
pol uacet al
6
CH2 OH
5
OH
O
4 1
OH
OH
3 2
OH
OH
OH
OH
HO O
6
OH
CH2 OH
5
OH
O OH
4 1
OH
3 2
OH
Mutarotation
C1 – anomeric C atoms
Anomers – aldose
isomers having
different configuration
at C1 atom (alpha and
beta)
Mutarotation can be
observed by
polarimeter
Changing configuration on one of chiral C-atoms will change optical properties of the
sugar – each anomer has specific angle of rotation of polarized light.
Mutarotation describes phenomenom of alpha to beta configuration (C1)
interconvertion.
Mutarotation
Glucose is a mixture of - and -anomers. The optical
rotation of the -anomer is +112.2° (c = 10% in water,
20 °C) and the -anomer is +18.7° (c = 10% in water, 20
°C). When D-glucose is dissolved in water, the optical
rotation gradually changes (mutarotates) with time and
approaches a final equilibrium value of +52.7° (c = 10%,
20 °C) due to the formation of an equilibrium mixture
consisting of approximately one-third - and two-thirds
-D-glucose.
Example:
What would be the optical rotation of the hypothetical
glucose solution consisting of 80% alpha and 20% beta-
anomers in equilibrium?
CH2 OH H CH 2OH OH CH OH
2
OH O O
C O
OH
OH OH OH OH
OH OH
OH H O OH O
C O
OH OH OH
OH
OH OH OH OH OH OH
HAWORTH-projection formulae
HC O
CH2OH O OR CH2 OH O O
CHOH
H
CHOH + H2O
ROH
OR
CHOH OH OR
CH 2OH OH OH OH OH OH OH
% compostion of water solution of aldoses at equilibrium at 40oC
Arabinose 63 34 3
Xylose 33 67 <1
Lyxose 71 29 <1
Alose 18 70 5 7
Altrose 27 40 20 13
Glucose 36 64 <1
Manose 67 33 <1
Galactose 27 73 <1
Talose 40 29 20 11
Structure
Configuration
Configurational isomers can interconvert only through breaking and reforming of
covalent bonds.
Conformation
Conformational isomers have identical molecular formula and configuration.
Conformational isomers (or conformers or rotational isomers or rotamers) are
stereoisomers produced by rotation (twisting) about σ bonds, and are often rapidly
interconverting at room temperature.
p orbitals of
oxygen
HO
O
OH OMe
O
HO
HO
OMe OH OH
metil-α-D-glukopiranozid
OH OH
HO
OH
O
OR
O
HO OH
HO
OH OR α-D-idozid
OH OH
HO
OH
O
OR
O
OH
HO
OH OR OH
α-D-altrozid
CHO CHO
H OH HO H
CHO CHO
H OH HO H
HO H H OH
HO H H OH
H OH HO H
H OH HO H
H OH HO H
CH2 OH CH2 OH
H OH HO H
CH 2OH CH 2OH
I II
D-(+)-glucose L-(-)-glucose
compound name example
monosaccharide
HOCH2(CHOH)nCHO aldose glucose
Monocarboxylic acid
HOCH2(CHOH)nCOOH Aldonic acid Gluconic acid
Dicarboxylic acid
HOOC(CHOH)nCOOH Aldaric acid Glucaric acid
polyhydroxyalcohol
HOCH2(CHOH)nCH2OH alditol sorbitol
Aldehyde acid
HOOC(CHOH)nCHO Uronic acid Glucuronic acid
COOH
Br 2 + H2O
(CHOH)n
CH 2OH
CHO
Aldonic
aldonska acid
kiselina
(CHOH)n
CH 2OH
aldoza
aldose COOH
HNO3
(CHOH)n
COOH
Aldaric acid
aldarna kiselina
HO
HOH2C O HO
HOH 2C O
CH3OH, HCl
HO OH HO OCH 3
OH OH
β-D-(+)-glucose Metil-β-D-glucoside
Reducing sugar Non-reducing sugar
Reactions of reducing sugars
When silver cation is the oxidant, as in the above equation, it is reduced to metallic
silver in the course of the reaction, and this deposits as a beautiful mirror on the
inner surface of the reaction vessel. The Fehling and Benedict tests use cupric cation
as the oxidant. This deep blue reagent is reduced to cuprous oxide, which
precipitates as a red to yellow solid. All these cation oxidations must be conducted
under alkaline conditions. To avoid precipitation of the insoluble metal hydroxides,
the cations must be stabilized as complexed ions. Silver is used as its ammonia
complex, Ag(NH3)2(+), and cupric ions are used as citrate or tartrate complexes.
Formation of ethers
methyl-β-D-glukoside methyl-β-2,3,4,6-tetra-o-methyl-glucoside
Non-reducing sugar Non-reducing sugar
6
CH2OH
5C O
H H
H
4
C C α-D-gluco-piran-ose
OH H 1 OH 1 2 3 4 5
OH
C C
3 2
H OH
1 - C-1 (α or β)
2 – stereochemistry of chiral C atom with the highest number (D ili L)
3 – stereochemistry of other C atomes (C-2, C-3, C-4, C-5)
4 – size of hemiacetal ring (furan or piran)
5 – simple sugar or derivative
Relative sweetness of
diferent carbohydrates
fructose 173
invert sugar 120
sucrose 100
xylitol 100
tagatose 92
glucose 74
sorbitol 55
mannitol 50
trehalose 45
regular corn syrup 40
galactose 32
maltose 32
lactose 15
O
H
C O
HOH2C
HO H
HO OH
L-askorbinska kiselina
AMIGDALIN
Indikan – prekursor indigo boje
CH 2 OH
O
O
OH
OH
N
H Indikan
OH
Hesperidin – flavonoid, antioksidans
HESPERITIN
RUTINOSE
CHO CHO CHO
CH 2
CH 2OH CH 3 CH 3
CH 2
H3 CO OCH 3 H3 CO
CH 3 CH 3 CH 3
CH 2 CH 2 CH 2
CH 3 CH 3 CH 3
O
OH OH
OH OH
OH R2
O O O
O
OH OH OH
OH
O
OH OH R1
a. R1=OH ; R2=H
OH OH OH b. R1=H ; R2= OH
OH
OH O
OH OH
H OH
o
O O
OH H O OH OH
O
HO O
O OH raf inoza OH
HO HH OH
OH H OH O
H O OH OH
OH H O
OH OH
2 HO H
trehaloza H OH
maltoza
H OH
30 %
70 %
Cellulose – structural plant
polysaccharide
Celobiose is monomeric
disaccharide
Dextranes
n around 35 –
inulin
n around10 –
oligofructose
Chitin – structural
polysaccharide
3D structure of amylose
(component of starch)
Nomenclature
Carbonyl group
Reduciton of metal ions
Reactivity
Basis for analysis
Hydrolysis and fermentation
undesirable
- foods darkness
- and off-flavor development
- loss of nutrition component (Lysine)
the Maillard reaction can seriously lower the nutritive
value of the food.
Toasting, for example, may reduce to one-half the
protein efficiency ratio of bread.
How to measure
browning
How to measure browning
As the thermal treatment resulted in the increase in
colored substances content, which is measured as an
increase in absorbance at 420 and 560 nm by reactance
colorimetry A420.
1- Water activity (aw)