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CARBOHYDRATES
Lecture Class of Dr. Carmen P. Sanchez
I. Definition
Carbohydrates chemically defined as polyhydroxyaldehydes or ketones and
their derivatives. There is more carbohydrate material in nature than all organic
substances combined.
Carbohydrates are also known as saccharides. They are made up only of
10% of the organic matter of the living cell.
Carbohydrates are the most abundant constituent of many foods and are
the source of a large part of the heat and mechanical energy of the body.

II. Importance
1. Preferential source of energy by the body tissues
2. A form of stored chemical energy.
3. Form of structural units within the cell
4. Other diverse functions – carbohydrates in combination with other
organic compounds become components of biologically important
substances
a. antigen-antibody interaction
b. filtration barriers
c. cell lubrication
d. protective cell coats
e. regulatory functions
f. transport functions
g. cell membrane components
h. blood coagulation
i. catalytic function
5. Source of carbon in the synthesis of other cell components

III. Classification of Carbohydrates

(Based on the number of saccharide units present in their molecules)

A. Monosaccharides-simple sugars; consist of a single polyhydroxy aldehyde or

ketone unit. Depending of the number of C.

1. Triose C3H6O3

- Aldotriose – with aldehyde group

Ex. Glyceraldehyde
- Ketotriose – with ketone group
Ex. Dihydroxyacetone

2. Tetrose C4H8O4

- erythrose
- erythrulose

3. Pentose C5H10O5
- xylose
- ribose
- deoxyribose
- arabinose
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- rhamnose

4. Hexose C6H12O6
- glucose
- galactose
- mannose
- fructose

5. Heptose C7H14O7
- mannoheptose
- mannoheptulose

The important monosaccharides are the pentoses and the hexoses.

a. Pentoses
Aldopentose – ribose
Ketopentose – deoxyribose

b. Hexoses
Aldohexoses – glucose, galactose, mannose
Ketohexoses – fructose

B. Oligosaccharides – with chains of 2 to 6 monosaccharide units linked

together
by glycosidic bonds. Most important member are:

1. Disaccharides
Sucrose = glucose + fructose
Lactose = glucose + galactose
Maltose = glucose + glucose

2. Trisaccharides
Raffinose - glucose + galactose + fructose

[Disaccharides and trisaccharides are sweet; starches and cellulose are tasteless]

C. Polysaccharides
They consist of long chains of monosaccharide units in a linear or
branched arrangement. They yield more than 6 molecules of
monosaccharide on hydrolysis.

1. Homopolysaccharides - polymers of a single monosaccharide

Ex. Starch group
- starch
- glycogen
- inulin
- dextrin

Cellulose group
- cellulose
- hemicellulose
- pentosan (gum arabic)
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- hexosan ( agar-agar)
- hexopentosan

2. Heteropolysaccharides - contain more than one kind of

Monosaccharide

D. Derived Carbohydrates - derivatives resulting from conversion to

compounds
by chemical reactions.
Ex. 1. Sugar acids
2. Sugar alcohol
3. Sugar amines
4. Deoxysugars
5. Glycosides

IV. Structure of Carbohydrates

The Conventions for representing carbohydrates
A. Fischer or Linear Projection
B. Haworth Projection or Ring structure

The Fischer or Linear Projection –

- open chain in a vertical manner
- lowest numbered carbon at the top
- most oxidized end of the molecule has the lowest number

CHO CHO CHO CH2OH

I I I I
H – C - OH HO – C - H H – C – OH C=O
I I I I
HO – C – H HO – C – H HO – C – H HO – C –H
I I I I
H – C – OH H – C – OH HO –C – H H – C – OH
I I I I
H – C – OH H – C –OH H – C – OH H – C – OH
I I I I
CH2OH CH2OH CH2OH CH2OH

Glucose Mannose Galactose Fructose

Haworth Projection or ring structure (hexagonal or pentagonal formula)

1. Cyclic or ring structure is formed between the aldehyde and an
alcohol
to form a hemiacetal bond or between a ketone and an alcohol to form
hemiketal.
The formation of the ring structure creates another asymmetric C
(C1-
anomeric C ) and the sugar can therefore exist in 2 stereoisomers forms
(anomers). The phenomenon of Mutarotation strongly supports that
sugar
exist in cyclic forms in solution.
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C HO – C
I I
H – C – OH H – C – OH
I I
HO – C – H o HO – C – H o
I I
H – C – OH H – C – OH
I I
H–C H–C
I I
CH2OH CH2OH

Alpha D – glucose beta D – glucose

2. Hexagonal or pentagonal formula

Rules in transforming cyclic to hexagonal:

a. those on the right side - below
b. those on the left side - above

Alpha-D-glucopyranose Beta-d-glucopyranose Fructofuranose

Terminologies:
1. D and L configuration – determine the orientation or position of the H and OH
groups around the C atom adjacent to the terminal 1o alcohol.
Where: If the OH is on the right side – D isomer
If the OH is on the left side – L isomer

Both D and L sugars of the same compound have identical properties such as
boiling points and solubilities in various solvents but they differ in optical
activity.

2. Asymmetric C – the carbon atom with 4 different substituents attached to its 4

valences.
Isomerism depends upon the number of asymmetric carbon atoms
The number of possible isomers of a compound depends on the number of
asymmetric carbon atoms (n) and is equal to 2n.
Glucose = 24

3. Optical Activity – shown by asymmetric C wherein if a beam polarized light is

passed in a solution of an optical isomer, it will rotated on the right. (d) or (+),
or to
the left (l) or (-).
Sugar is: Dextrorotatory – plane of polarized light is rotated clockwise
Levorotatory – if counterclockwise
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4. Stereoisomers – compound with the same structural formula but with a
different
spatial configuration.
- substituent on the same side – Cis
- substituent on the opposite side – Trans

5. Epimers – isomers differing as a result of variation in configuration of the OH

and H
on carbons 2,3 and 4.
Ex. Glucose is an epimer to mannose on C2
Glucose in an epimer to galactose on C4

6. Mesostructure – isomers which are optically inactive due to internal

compensation

7. Racemic or DL mixture – mixture of equal amount of D and L isomers and

exhibits
no optical activity.

8. Anomers – pair of stereoisomers differing on the orientation of OH on the

anomeric
carbon which is C . Anomers are pairs of stereoisomers which are related to
each
other.
Ex. Alpha-D-glucopyranose and Beta-D-glucopyranose

IV. Importance of Carbohydrates and their Characteristics

A. Monosaccharides
1. D-Glucose
- Also called dextrose or grape sugar
- Yellowish white or colorless, crystalline, freely soluble in water
- found in fruit juices, formed by complete hydrolysis of starch
- the only sugar present in the blood about 0.1%
- has reducing property, forms osazone and saccharic acid
- fermented by yeast
- in diabetes mellitus, glucose is increased in the blood and finds
its
way into the urine

2. D-Fructose
- also called levulose or fruit sugar
- the sweetest sugar, 173.3% sweet
- found in fruits, vegetable, honey
- prepared by hydrolysis of inulin
- can be converted to glucose in the liver
- has reducing property and forms osazone
- also found in the urine of patients with diabetes mellitus
- gives a cherry red color with Seliwanoff’s resorcinol HCl reagent

3. D-Mannose
- produced upon hydrolysis of plant mannose and gums
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- sugar frequently found in glycoproteins
- constituent of prosthetic polysaccharide of albumin and
globulin
- has reducing property, may form osazone

4. D- Galactose
- found in plants as pectin
- less sweet and less soluble than glucose
- galactose + glucose = lactose (milk sugar)
- can be changed to glucose in the liver
- has reducing property, forms a characteristic osazone crystal
- with HNO3 forms an insoluble mucic acid
- not fermented by yeast
- appears abnormally in the urine of nursing infants suffering from
digestive disturbances

B. Disaccharides
1. Maltose
- Intermediate product of the action of amylase on starch
- relative sweetness is 32.5%
- sweet, crystalline, fermented by yeast
- produces osazone crystal

2. Lactose
- also called milk sugar
- yields glucose and galactose on hydrolysis
- beta lactose has been recommended for infant feeding
- a reducing sugar
- sour milk that is formed after the conversion of lactose into
lactic
acid by microorganisms.

3. Sucrose
- most important sugar from the dietary standpoint
- 100% sweet
- also called cane sugar, disaccharide of glucose and fructose
- no reducing property, no free anomeric carbon
- no reaction to phenylhydrazine to form osazone
- no mutarotation, readily hydrolyzed yielding a crude mixture
called invert sugar because of the strongly levorotatory
fructose
- an inert sugar because the –CHO group in its structure is linked
with the ketone group of fructose

C. Polysaccharides
Most complex, white, tasteless, amorphous compounds
Non-fermentable by yeast, mostly antigenic

1. Starch
- makes 50-70% of the solid substance of most cereals
- found in cereals, potatoes, legumes, some vegetables, some
bulbs, tubers
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- insoluble in water, gives a blue color with iodine solution
- constituents:
a. amylase – 15-20% non branching helical structure
responsible
for the deep blue color with iodine
b. amylopectin – 80-85% $
branch chain that gives red color with iodine
because they do not coil effectively.
2. Glycogen
- also called animal starch, storage polysaccharide
- gives red color with iodine
- yields maltose on hydrolysis with maltase
- its molecule is highly branched, molecular weight is very high
(1-
5M)
- found mostly in the liver as storage material and in the muscles
as
source of energy

3. Inulin
- found in tubers, roots of dalias, garlic, onions
- soluble in hot water, no reaction with iodine
- used for the determination of GFR

4. Dextrins
- intermediary product of starch hydrolysis
- Erythrodextrin gives a red color with Iodine as it reaches certain
degree of branching on hydrolysis
- as hydrolysis proceeds, the red color disappears assuming the name
achrodextrin
- used as a mucilage as those at the back of stamps
- widely used in infant feeding because when mixed with milk, the
formation of large, heavy curds on milk in the baby’s stomach is
prevented

5. Cellulose
- chief framework constituent of plants
- cannot be digested by humans due to the beta linkage and therefore
forms a bulk in the diet
- no reaction with iodine, insoluble in water
- furnishes roughage which stimulate peristalsis, thus promoting the
evacuation of the bowel
- it is constructed solely from glucose units joined by beta 1-4 linkages

6. chitin
- found in the shells of crustaceans, exoskeletons of insects

7. others
- Glycosaminoglycans – intercellular substance in tissues
- Glycoproteins – sugar conjugated to proteins
- Sialic acid – found in human ganglioside
- These serve as biological lubricants
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D. Derived Monosaccharides
They contain functional groups other than carbonyl and hydroxyl groups.
These are the carbohydrates converted to compounds by chemical reactions.
Upon oxidation, sugar acids result upon reduction sugar alcohols are derived.

1. Sugar Acids
a. aldonic acid – aldehyde group is oxidized
ex. Glucose to gluconic acid or aldonic acid

b. Aldaric Acid - both aldehyde and primary alcohol groups are oxidized
ex. Glucose to saccharic acid or aldaric acid

c. Uronic acid – primary alcohol is oxidized

Ex. Glucose to glucoronic acid

2. Sugar alcohol - reduction of sugars to sugar alcohol

a. Glucose - sorbitol or glucitol
b. Mannose – mannitol
c. Galactose – Dulcitol or galactitol

VI. General properties of Carbohydrates

A. Physical Properties
1. mono and disaccharides are white crystalline substances;
starches are amorphous powder while cellulose is fibrous
2. mono and disaccharides are readily dissolved in water
3. mono and disaccharides are sweet; starch and cellulose are
tasteless

B. Chemical Properties
1. Reducing Action
Forms the basis for both qualitative and quantitative test for
sugars. Sugars that contain free aldehyde or ketone group possess
reducing properties. These reducing action is manifested by color changes
or precipitation when the sugar solution is heated with alkaline solutions of
metals. Among these tests are:

a. Fehling’s or Benedict’s test

Cu(OH)2 →Cu2 O + 2 H2O + O2

b. Tollen’s test or silver mirror test

2AgOH + R-CHO → 2Ag + R-COOH + H2O

c. Nylander’s test
2Bi (OH)3 → 2Bi + 3O + 3 H2O

d. Picric Acid test

C6H2OH (NO2)3 → C6H2OHNH2 NO2)2

e. Barfoed’s test – distinguishing mono from disaccharides cupric acetate

in
acetic acid → cuprous oxide
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2. Osazone Formation
All sugars except sucrose form yellow crystalline osazone
crystals when treated with excess phenyl hydrazine. The individual sugar
maybe identified by the characteristic structure and melting point of the
osazone formed.

3. Fermentation
It is the breaking down of complex substances by the use of
enzymes. All sugars, except lactose and most polysaccharides undergo
fermentation through the aid of specific enzymes, yeast is commonly used
to produce fermentation in sugars.

4. Action of alkalis
Moore’s Test
When a solution of reducing sugar is heated with an alkali
(NaOH), it turns yellow to orange and finally dark brown,
liberating
the odor of caramel.
This is due to the liberation of aldehyde which
subsequent
polymerizes to form a resinous substance, caramel.
Glucose, fructose or mannose when allowed to stand in
the
presence of weak alkali (BaOH) is converted into a mixture
containing all the three sugars and whichever one of them is
used
the same proportion of the three sugars is always reached at
equilibrium. This tautomeric change is known as Lobry de
Bruyn
von Eckenstein transformation, in which anyone sugar is readily
converted to the other two forms.

5. Action of Acids
a. dilute acids ---- hydrolysis
b. strong mineral acids

monosaccharides with concentrated acids and at boiling

temperature are dehydrated forming:

pentose → furfural
hexose → hydroxymethyl furfural and its derivatives

These condense with a number of compounds to yield colored

products.

a. Molisch’s test ( a general test for carbohydrates)

When sugar solution is treated with Molisch’s reagent
(alpha naphtol) and concentrated H2SO4, a violet color forms at
the junction of the two liquids.

b. Seliwanoff’s Test
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This is a specific test for ketose sugar like fructose which
forms rapidly hydroxymethyl furfural as a result of dehydration.
This
condenses with resorcinol to form red colored compounds.

c. Iodine Test
With iodine, uncooked starch gives a violet color but
cooked starch forms a blue color heating makes the color
disappear but the blue color returns on cooling.

d. Anthrone test
A blue or green color is produced with anthrone reagent
and concentrated sulfuric acid with sugar.

e. Bial’s Orcinol HCl test

A green solution is produced with HCl and orcinol reagent
with pentoses.

f. Tauber’s Benzidine test

A violet color is produced with benzidine + sugar.