CARBOHYDRATES (or Glucides, from Greek glucos, sweet)

• They are the most abundant and spread organic compounds on earth.

• They have a central role in the metabolism of plants and animals.

• Their biosynthesis in green plants, i.e. photosynthesis, starting from CO2 and H2O, in
presence of light, is the existence base of all the other organisms.

• They are the basic constituents of many foods representing a large portion of the total
intake of nutrients in human diet (40-75% of the daily energy intake).

• Also non digestible carbohydrates are important in a balanced daily diet.

• Carbs have other important functions in foods (beyond the energetic):

-they act as sweetening;

-as gel- and paste- forming;

-as thickening;

-as stabilizers;

-they are forerunners of aromatic substances and colorants which are formed in the food
during production and subsequent processes (also cooking). 1
Carbohydrates can be defined as polyhydroxy aldehydes, ketones, alcohols, acids,
their simple derivatives and their polymers having acetal type linkages.

They may be classified according to their degree of polymerization and may be divided
into three principal groups, namely sugars, oligosaccharides and polysaccharides.

Carbs chemical formula: Cn(H2O)n

This is a simplification, there are other molecules having different formula but reacting as
carbs, thus belonging to the same category (e.g. deoxysugars, aminosugars, sugars with
carboxyl moiety).
CLASSIFICATION
Class (DP*) Sub-Group Some components

Monosaccharides Glucose, galactose, fructose

Sugars (1-2) Disaccharides Sucrose, lactose

Polyols Sorbitol, mannitol

Malto-oligosaccharides Maltodextrins
Oligosaccharides (2-9)
Other oligosaccharides Raffinose, stachyose, fructo-oligosaccharides

Starch Amylose, amylopectin, modified starchs

Polysaccharides (>9) Non-starch polysaccharides Cellulose, Hemicelluloses, Pectins, β -
Glucans, Fructans, Gums, Mucilages2
DP * = Degree of polymerization
• Monosaccharides: polyhydroxy-aldehydes or -ketones with a linear carbon chain (3 to 8 carbon
atoms); e.g.: glucose, fructose and galactose;

glucose

fructose galactose
• Oligosaccharides: formally derived from the condensation of monosaccharides, with H2O elimination;
disaccharides: sucrose, maltose, lactose; trisaccharides: raffinose; tetrasaccharides: stachyose;

raffinose

lactose

• Polysaccharides: polymers with high MW,

having different characteristics with respect to
other carbs; often insoluble in H2O, they are
not sweet and they are somewhat inert; e.g.:
starch, cellulose, pectins.

cellulose
(portion) 3
Total sugar in Food Total sugar (%)
various foods Vaccine milk 4,8
Human milk 7,2
Cheese 0,1-0,9
Yoghurt 7,8
Fruit yoghurt 15,7
Ice cream 22,2
Apples 11,8
Banana 20,9
Grape 15,4
Oranges 8,5
Honey 75
Jam 50-70
Chocolate 60
Beer 1,5-2,3
Wine 0-5
Dessert wine 5-15 4
Sugars distribution in fruit and vegetables

Tomatoes Glucose
Mais
Soy Fructose
Pineapple
Orange juice Sucrose
Onions
Grapes Maltose
Figs
Carrots Galactose
Cabbages
Bananas Stachyose,
Apples Raffinose,
Verbascose
0% 20% 40% 60% 80% 100%
5
MONOSACCHARIDES
NOMENCLATURE
The suffix –ose indicates the presence of the carbonyl moiety in an hydroxylated carbon chain.

ALDOSES: polyhydroxyaldehydes KETOSES: polyhydroxyketons deriving

deriving formally from glyceraldehyde by formally from dihydroxyacetone by the
the addition of –CH-OH units (they can addition of –CH-OH units (they can be
be triose, tetrose…). triulose, tetrulose,… ); the position of
H carbonyl is specified by a numeric prefix
O (usually is in position 2).
CH2OH

H OH
suffix: -ose O suffix: -ulose
CH2OH
CH2OH

If two carbonyl moieties are present:

-the molecule can be a dialdose (two aldehydes groups);
-or osulose (one aldehyde and one ketone group);
-or diulose (two ketone groups).
When –OH is substituted by –H, the molecule is a deoxysugar, when –OH is substituted
by –NH2, the molecule is an aminodeoxysugar. 6
CYCLIZATION
All the monosaccharides starting from tetroses and 2-pentuloses cyclize to five and six
membered lactols (furanoses from furan, and pyranoses, from pyran) respectively by
intramolecular hemiacetal (or hemiketal) formation.

With the exception of erythrose, monosaccharides crystallize in cyclic forms; in solution there
is an equilibrium between the open chain and the cyclic forms, the second being
predominant.

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CONFIGURATION
ALDOSES
Glyceraldehyde has a chiral center, thus it exists as a pair of enantiomers, D and L forms.

From D-glyceraldehyde it is possible to obtain a mixture of D-erythrose and D-threose,

while from L-glyceraldehyde a mixture of L-erythrose and L-threose is obtained.
CN CN
CHO O O
+ OH OH
H OH HO H 1) H
HCN H H H OH
H OH + +
H OH H OH 2) NaHg/NaBH4
CH2OH
OH OH OH H
CH2OH CH2OH
D-glyceraldehyde
D-erythrose D-threose
8
Through the cyanhydrin reaction, starting from D-glyceraldehyde two D-tetroses are
obtained and from each of them two D-pentoses, and so forth; thus from D-
glyceraldehyde 8 hexoses belonging to the same D-series can be obtained.

CHO
H OH D-glyceraldehyde (D-glycero-)
CH2OH
CHO CHO

D-erythrose (D-erythro-) H OH HO H D-threose (D-threo-)

H OH H OH
CH2OH CH2OH

CHO CHO CHO CHO

H OH HO H H OH HO H
H OH H OH HO H HO H
H OH H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH
D-ribose D-arabinose D-xylose D-lyxose
(D-ribo-) (D-arabino-) (D-xylo-) (D-lyxo-)
CHO CHO CHO CHO CHO CHO CHO CHO
H OH HO H H OH HO H H OH HO H H OH HO H
H OH H OH HO H HO H H OH H OH HO H HO H
H OH H OH H OH H OH HO H HO H HO H HO H
H OH H OH H OH H OH H OH H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH
D-allose D-altrose D-glucose D-mannose D-gulose D-idose D-galactose D-talose
(D-allo-) (D-altro-) (D-gluco-) (D-manno-) (D-gulo-) (D-ido-) (D-galacto-) (D-talo-)9
 An important aldoses degradation reaction takes place via disulfone formation
starting from the dithioacetal.
CHO CH(SEt)2 CH(SO2Et)2 CH2(SO2Et)2
+ -
EtSH, H RCOOOH OH +
CHOH CHOH CHOH HC O

R R R R
Epimers: two molecules differing only for the configuration of a chiral center, e.g. D-
glucose and D-mannose.
Occurence of aldoses

10
KETOSES Name, structure Where is it found?
hexulose
D-fructose vegetables, honey
D-psicose residues of fermented
molasses
Eptulose, octulose,
nonulose
D-manno-2-heptulose avocado
D-glycero-D-manno-2- "
octulose
D-erythro-L-gluco-2- "
nonulose

L series??
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SYSTEMATIC NOMENCLATURE

ALDOSE
If the number of C atoms is <=6, traditional name can be used, otherwise the molecule
portion adjacent to the carbonyl is assigned the maximum possible prefix and the remaining
portion of the molecule, (if constituted at least by 2 C atoms), another prefix is assigned and
this is named first; then the name is written depending on the total of C atoms.

Examples:

CHO CHO
H OH H OH
H OH
H OH
H OH H OH L-manno-
HO H HO H
HO H
H OH HO H
H OH
HO H
H OH HO H
H OH
H OH
CH2OH
CH2OH H OH D-glycero-
D-glucose or D-gluco- D-glycero-L-manno-
D-gluco-hexose heptose
KETOSE
If it contains less than 4 chiral carbons, traditional name can be used, otherwise the groups
12
adjacent to the carbonyl must be considered:
The longest of the two portions adjacent to carbonyl is named first:

HO H
HO H
L-glycero-
HO H
H OH HO H
HO H
H OH H OH
H OH

D-arabino D-threo- D-lyxo-

Fructose D-threo-L-glycero-
3-hexulose
or D-arabino-2-hexulose or
D-lixo-3-hexulose
When sugar cyclizes to lactol, a new chiral center is formed, thus two diastereomers
(anomers) are formed, named α and β anomers.

glucose α-D-glucopyranose β-D-glucopyranose

13
 [α]20D= [α]20D= +19°
°
+110°°
64%
36%
At equilibrium:
All the monosaccharides can [α]20D= +52,53°°

exist in solution in five forms:

<1%

Cyclic forms are much favoured with respect to open chain forms.
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Generally, the favourite cyclic form, more stable, is the pyranosic one.
PHYSICAL PROPERTIES
1. OPTICAL ROTATION AND MUTAROTATION

Non racemic chiral compounds deviate polarized light by an angle α proportional to their
concentration in the solution.
100 ∗ α
[α ]λt
=
α = deviation angle at T °C;
l ∗c
l = polarimetric tube length (dm);
c = grams of optically active substance in 100 ml of solution;
α]tλ = specific rotation constant;
[α
λ = selected wave length (generally sodium D-line light);
t = temperature at which the measurement is done (usually 20-25°C).

Obviously specific rotation for two anomers is different (and even for furanose
and pyranose forms of a same sugar); thus a solution of a pure isomer freshly
prepared has a rotation angle varying during time till it reaches a constant value
(at equilibrium among the various forms).
MUTAROTATION
PHENOMENON 15
2. Higroscopicity and solubility

• The amount of water kept by the sugars depends on the sugar structure, the isomers
present and the sugar purity.

• Solubility of mono- and oligosaccharides in water is good.

• Anomers can have very different solubility (e.g. α and β lactose).

• Monosaccharides have low solubility in ethanol and they are insoluble in organic
solvent such as benzene, ethyl ether, chloroform.

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SENSORY PROPERTIES
• Mono-, oligosaccharides and their alcohols are sweet (few exceptions);
• Main sweeteners: sucrose, glucose, fructose, invert sugar (glucose and fructose),
lactose and alcohols (sorbitol, mannitol, xylitol).
• Sugars differ in the quality of sweetness and taste intensity.
• As oligosaccharides dimension increases, their sweetness power decreases.
• The taste intensity can be quantificated by determining the minimum level of
concentration at which the sweet taste is still detected or referring to a reference
solution (usually sucrose).

Limit of Relative Relative

Sugar Sugar Sugar
detection % sweetness sweetness
Fructose 0.24 Sucrose 100 D-Mannitol 69
Glucose 1.17 D-Glucose 69 D-Mannose 59
D-Galactose 63 Raffinose 22
Lactose 2.60
D-Fructose 114 D-Ramnose 33
Maltose 1.36
Invert sugar 95 D-Sorbitol 51
Sucrose 0.36 Maltose 46 Xylitol 102
Lactose 39 D-Xylose 67

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• The minimum value depends on the affinity between the substance’s structure
and the chemoreceptor sites for sweetness.
• Further parameters influencing the quality and intensity of sweetness are: pH,
temperature, presence of other compounds.

Temperature dependance
of relative sweetness of
some sugars
• There is also a relation between sugar content
Relative sweetness

and volatiles compounds.

• Also the color of the solution can influence the
fructose organoleptic evaluation.

glucose
galactose
maltose • Composition and concentration of sweetener
must be carefully evaluated in each food
formulation to give an optimal sensory result.
Temperature (°
°C)

Need of an AH (H donor) B (H acceptor) X

(hydrophobic site) system in a substance in
order to give sweet taste.
D-glucopyranose
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 REACTIVITY
1) REDUCTION to ALCOHOLS
• NaBH4

• electrolysis

• catalytic hydrogenation

Alcohol name: in the sugar name –ulose or –ose is substituted with –itol.

Xylitol (pentose), sorbitol (naturally found in many fruits), D-mannitol are used in diet
formulations, to decrease water activity, as softeners, etc. They afford 2,4 Kcal/g.

2) a. OXIDATION to ALDONIC ACIDS

β-D-glucopyranose

NAME: ALDOSE ALDONIC ACID

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2) b. OXIDATION to ALDARIC ACIDS

Stronger conditions (e.g. HNO3) allow oxidation of both the terminal carbons of
aldose:

It can form mono or dilactones

NAME: ALDOSE ALDARIC ACID (dicarboxylic acid)

2) c. OXIDATION to URONIC ACIDS

To oxidize saturated terminal carbon only, the carbonyl moiety of the aldose
must be protected; then, after deprotection, the uronic acid is obtained.

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Uronic acids are widespread in nature, forming polysaccharides (e.g. pectines) having
industrial applications as gel-forming.

3) REACTION in BASIC and/or ACIDIC MEDIA

• Monosaccharides are stable in a pH range of 3-7 (if compounds with amino

groups are not present).

• At low pH enolization followed by H2O loss, predominates.

• At very high pH, enolization followed by chain fragmentation, predominates.

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3) a. REACTION in STRONGLY ACIDIC MEDIUM

• Disaccharides and oligosaccharides are formed (intermolecular glycosidic

bond).

• When the monosaccharide conformation is proper a glycosidic intramolecular

bond can be formed.

• Warming in acidic medium, enolization, dehydratation, formation of

substituted furans and pyrans take place:
H

HC O HC O HC O HC O
OHC OH CHO
H OH OH O H O
H

HO H HO H - H2O H - H2O H - H2O

O O
H OH H OH H OH H

H OH H OH H OH H OH CH2OH
CH2OH

CH2OH CH2OH CH2OH CH2OH

HMF (Hydroxy
Where is the Methyl Furfural)
mistake??? 22
3) b. REACIONS in STRONGLY BASIC MEDIUM
• In strongly basic medium aldose and ketose enolise quickly, thus fructose, mannose and
glucose equilibrate by the formation of the shared 1,2-enediol.

• In presence of O2 or other oxidants (Cu2+) the double bond C,C breaks forming
carboxylic acids.

The method is applied to the quali- quantitative determination of reducing sugars.

• Anyway also other transformations can take place leading to formation of several volatile
compounds.

• Acetic acid
Some of the volatile
compounds formed • Hydroxyacetone
warming up Cyclopentenolones are
• Hydroxybutanone
fructose syrup at
typical compounds with
pH 8-10 for 3 h. • Furfurylalcohol
“caramel like” aroma
• 5-Methyl-2-furfurylalcohol
O
• γ-butyrolactone

HO
• Various cyclopentenolones

H3C 23
NON ENZYMATIC BROWNING
Sugars contribute to the organoleptic characteristics of a food not only by their presence, but
also by the products of their degradation.

Caramelization (neutral or basic/acidic catalysis, high temperature, sugars)

Maillard reaction (neutral or basic/acidic catalysis, high temperature, sugars, amino groups)
O NR NHR NR O
O
RNH2 OH -H2O OH -NH2R O O
OH OH HOH2C
H
HO HO HO CH2

enaminol HMF
glucide Schiff base

NHR
Amadori compound
O

HO

Browning is due to the polymerization of

N N N
R
many molecules having low MW. R R

Polymers formed (melanoidins) have X X

X=O, NR

structures as the following: 24

Aroma compounds are formed: lactones, furanons, pyranons, aldehydes, etc.
O CH3 H3C O HO CH3
CH3

Sotolon (typical aroma of

brown sugar).
OH O CH3
HO O O

Negative aspects:
• Milk browning;
• Loss of essential aminoacids;
• Formation of potentially carcinogenic compounds (heterocyclic amines);
• Formation of aroma not always good (acrolein, piruvic aldehyde, glyoxal, etc.).
Positive aspects:
Formation of desirable aroma (toasting of coffee, cooking of food, etc.);
Formation of colour compounds (cooking of bread, of meat);
Formation of antioxidant compounds that protect the food against oxidation.

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