Sugars

Carbohydrates
 Carbohydrates:
 Monosaccharides

 Aldoses and ketoses

 3-9 C atoms, deoxysugars, brainched, aminosugars…
 oligosaccharides

 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.

Refractive index is a physical property of any compound in

solution while specific rotation of polarized light is a
property of only optically active compounds
Aldoses

 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

Aldose α-piranose β-piranose α-furanose β-furanose

Ribose 20 56 6 18

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

Gulose <22 >78 <1

Idose (at 60oC) 31 37 16 16

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

Normal conformer (C1) alternative conformer (1C)

 O O
OR

manje stabilan stabilnije

Less stable more stable conformer
OR
 OH
HO

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

 Useful tests for aldehydes, Tollens' test, Benedict's

test & Fehling's test, take advantage of this ease of
oxidation by using Ag(+) and Cu(2+) as oxidizing agents
(oxidants).

RCH=O + 2 [Ag(+) OH(–)] RC(OH)=O + 2 Ag (metallic mirror) + H2O

 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

HOH 2C (CH3) 2SO4 HOH 2C

HO
O H 3CO
O
NaOH

HO OCH3 H 3CO OCH3

OH OCH 3

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

D-Glucose L-Rhamnose D-Digitoxose

CHO CHO CHO

CH 2

H3 CO OCH 3 H3 CO

CH 3 CH 3 CH 3

D-Digitalose L-Thevetose D-Diginose

CHO CHO CHO

CH 2 CH 2 CH 2

OCH 3 OCH 3 OCH 3

CH 3 CH 3 CH 3

L-Oleandrose D-Sarmentose D-Cymarose

SOME SUGARS IN CARDIAC GLYCOSIDES
HO
HOH 2C O HO
HOH 2 C O
+ = 11 Isomeric
HO
OH
HO
OH
disacharides
OH,,H OH,H
D-Glukoza D-Glukoza

α (1→ 2) β (1→ 2) α (1→ 1) α

α (1→ 3) β (1→ 3) α (1→ 1) β
α (1→ 4) β (1→ 4) β (1→ 1) β
α (1→ 6) β (1→ 6)
 OH

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

α-D-glucopiranosyl β-D- fructo furanosid a. celibioza a. celobiose

b. laktoza
saccharose b. lactose

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

trechalose maltose rafinose

Homopolysaccharides

a) Plant cell - starch; b) Animal cell - glycogen

Starch structure

30 %

70 %
 Cellulose – structural plant
polysaccharide

 Celobiose is monomeric
disaccharide
Dextranes

 Yeast and bacteria

Inulin – plant storage
polysaccharide

n around 35 –
inulin
n around10 –
oligofructose
Chitin – structural
polysaccharide
3D structure of amylose
(component of starch)
Nomenclature

 Polysaccharides are condensation

polymers
 Neutral monosaccharides
 Acidic monosaccharides
 Basic monosaccharides
 Nomenclature
 Homoglycans
 Glucose - glucan
 Manose - manan
 Heteroglycans (di-, tri-,…)
 D-galakto-D-manan
Reducing properties

 Carbonyl group
 Reduciton of metal ions
 Reactivity
 Basis for analysis
Hydrolysis and fermentation

 Fermentation will result in CO2, lactic acid, ethanol and

some minor components as well (propionic acid, butyric
acid).
Bifidogen molecule lactulose
present in heat treated milk
Non-Enzymatic
Browning
TABLE OF CONTENT
 INTRODUCTION
 Changes during non-enzymic browning
 Types of Non-enzymatic Browning
 Maillard Reaction mechanisms and products
 How to measure browning
 Kinetic of non enzymatic browning
 Controlling Factors of the Maillard Reaction
Products
 Prevention of non enzymatic browning
 CONCLUSION
Introduction

 Foods may develop a variety of brown colors, from

yellow-brown to red-brown to black-brown, during
handling, processing, and storage.
 These colors are desirable in certain foods (e.g., coffee, beer, bread,
maple syrup).
 In other foods, such as most dehydrated fruits and vegetables, dried
eggs, and canned or dried milk, browning is detrimental.
 Even when desirable, browning should not be excessive, as in potato
chips, French fries, and apple juice.
 Numerous reactions lead to browning in foods. Some of these may
also generate flavors and/or alter the nutritional properties of
foods.
enzymatic and nonenzymatic
browning
 Enzymatic browning
occurs when fresh food or beverage products are
exposed to air and there are active enzymes present
within the food or beverage product. When an apple
slice or banana turns brown, it is usually due to
polyphenol oxidase enzyme activity.
 Non-enzymatic browning
can produce brown, fluorescent, highly cross-linked
pigments, such as melanoidin chromophores.
Nonenzymatic
Browning
Types of Nonenzymatic
Browning

A number of chemical processes not involving enzymes

may result in food browning.
1. Maillard reaction
2. Caramelization
3. ascorbic acid browning
4. metalpolyphenol browning.
Changes during non-enzymic
browning
 this changes some times are
desirable and sometimes undesirable
 Produces flavor
 Produces color
 Produces antioxidant products
 Produces toxic products
 loss and Destroys nutrients (lysine)
 formation of undesirable products such
as HMF (5-hydroxymethylfurfural)
1. Caramelization

 This reaction leads to brown products when sugars are

heated dry or in solution.
 The large quantities of industrial caramel color that are
added to beverages (cola drinks), baked goods, and
confections are made by heating high-conversion corn
syrups in the presence of catalysts (acids, alkali).
Chemistry of caramelization

 The chemical transformations involved in

caramelization are complex and poorly understood.
 They include dehydration, fragmentation, and
polymerization.
 On the heating of pentoses, furfural is formed which
polymerizes to brown products.
 Heating hexoses results in hydroxymethylfur-fural,
which polymerizes similarly.
 Non-enzymatic browning reaction, one type of is
caramelisation
Dehydratation under acid
catalyzed caramelization
 Maltol and isomaltol are typical flavouring compounds
(breadtaste, flavor enhancer)
Fragmentation during
alkaline catalyzed
caramelization
 Hydrolysis of sucrose prior to caramelization\
 Ketoses are more reactive
2. Ascorbic Acid Browning

 When ascorbic acid is heated in the presence of acids,

furfural is formed.
 The latter, either by itself or after reacting with amino
compounds, polymerizes to brown products.
 Citrus juices, especially their concentrates, develop
browning, which has been attributed to ascorbic acid
degradation.
3. Metal-Polyphenol
Browning
 Polyphenolic compounds form complexes with certain
metals. The polyphenols of fruits and vegetables most
commonly chelate iron. The resulting iron complexes
are bluish black pigments.
 Cutting apples with a non-stainless-steel knife results in
darkening of both the blade and the surface of the
apple.
 This darkening is independent of the enzymatic
browning that might develop as a result of cutting.
4. The Maillard Browning

 Maillard reaction is caused by the

condensation of an amino group and a
reducing compound, resulting complex
changes in biological and food system.
 This reaction was described for the first
time by Louis Maillard in 1912.
Maillard reaction is:

 “The sequence of events that begins with reaction of

the amino group of amino acids with a glycosidic
hydroxyl group of sugars; the sequence terminates with
the formation of brown nitrogenous polymers or
melanoidins”
Maillard Reaction
mechanisms and
products
Maillard Reaction
mechanisms and products
 This reaction is actually a series of reactions occurring
from the first encounter of a carbonyl compound with
an amine compound to the formation of brown
pigments.
 It is also known as the carbonyl-amine reaction, and its
brown products are often called melanoidins, indicating
their visual similarity to the melanins of enzymatic
browning.
 The most common carbonyl compounds of foods
involved in the Maillard reaction are reducing sugars,
and the most common amine compounds are amino
acids.
 Among sugars, pentoses are more reactive than
hexoses, and hexoses are more reactive than reducing
disaccharides.
 When free amino acids react with sugars, lysine appears
to be the most active among them.
 Maillard reaction occurs when
virtually all foods are heated,
and also occurs during storage.
 Maillardreaction form products
that are desirable or
undesirable

desirable
- caramel aromas
- and golden brown colors,

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)

 Water is produced during Maillard reaction, thus the

reaction occurs less readily in foods with a high aw
values while, at low aw, the mobility of reactants is
limited, despite their presence at increased
concentrations.
 As the figure shown the Maillard reaction occurs most
rapidly at intermediate aw values (0.5-0.8),
 and aw is of most significance to the reaction in dried
and intermediate- moisture foods (IMFs), which have aw
values in this range.
 humectants, such as glycerol, can lower the aw value
for maximum browning.
 Energetically less preferable (5%)
 Energetically favorable (95%)

 Both pathways give alpha-dicarbonyl compunds wich are

very reactive and susceptible to nucleophilic addition
reactions
Strecker
degradation
 Pyrazines (aroma
components)
 Short chain aldehydes
(reactive, can be toxic, low
sensorial threshold value)
Acrylamide formation
Asparagine is the most common
precursor
Effect of pH and temperature

 pH: acidic pH will inhibit MR

 Increasing temperature favour MR
Adsorption isotherm of amporphous
raffinose at 27 oC

 Physical collapse of powder – amorphous raffinose will

be transformed to the crystalline raffinose-
pentahydrate by water uptake