CARBOHYDRATES

By: SIR RODEL C. ESPINO

MCNP-ISAP
BIOCHEMISTRY INSTRUCTOR

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 General characteristics of Carbohydrates

• the term carbohydrate is derived from the

french: hydrate de carbone
• compounds composed of C, H, and O
• (CH2O)n when n = 5 then C5H10O5
• not all carbohydrates have this empirical
formula: deoxysugars, aminosugars
• carbohydrates are the most abundant
compounds found in nature (cellulose: 100
billion tons annually)
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 General characteristics
• Most carbohydrates are found naturally in bound
form rather than as simple sugars
• Polysaccharides (starch, cellulose, inulin, gums)
• Glycoproteins and proteoglycans (hormones,
blood group substances, antibodies)
• Glycolipids (cerebrosides, gangliosides)
• Glycosides
• Mucopolysaccharides (hyaluronic acid)
• Nucleic acids
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 Biological Functions
• sources of energy
• intermediates in the biosynthesis of other
basic biochemical entities (fats and proteins)
• associated with other entities such as
glycosides, vitamins and antibiotics)
• form structural tissues in plants and in
microorganisms (cellulose, lignin, murein)
• participate in biological transport, cell-cell
recognition, activation of growth factors,
modulation of the immune system
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 Classification of Carbohydrates
• Monosaccharides (monoses or glycoses)
• Trioses, tetroses, pentoses, hexoses
• Oligosaccharides
• Di, tri, tetra, penta, up to 9 or 10
• Most important are the disaccharides
• Polysaccharides or glycans
• Homopolysaccharides
• Heteropolysaccharides
• Complex carbohydrates
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 Monosaccharides
• also known as simple sugars
• classified by 1. the number of carbons and 2.
whether aldoses or ketoses
• most (99%) are straight chain compounds
• D-glyceraldehyde is the simplest of the
aldoses (aldotriose)
• all other sugars have the ending ose (glucose,
galactose, ribose, lactose, etc…)
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Structure of a simple aldose and a simple ketose

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 Aldose sugars

H H H H H

C O C O C O C O C O

(H C OH)n H C OH H C OH H C OH H C OH

CH2OH CH2OH H C OH H C OH H C OH

Aldose Aldotriose CH2OH H C OH H C OH

n=1
Aldotetrose CH2OH
n=2 H C OH
Aldopentose
CH2OH
n=3
Aldohexose
n=4

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 Ketose sugars

CH2OH CH2OH
CH2OH
CH2OH
C O C O CH2OH
C O
C O
(H C OH)n H C OH C O
H C OH
CH2OH
CH2OH H C OH H C OH
CH2OH
CH2OH H OH
Ketose Ketotriose Ketotetrose
n=1 Ketopentose H C OH
n=0
n=2
CH2OH
Ketohexose
n=3

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 Enantiomers and epimers

H H
H H C O C O
C O C O HO C H HO C H
H C OH OH C H HO C H HO C H
H C OH OH C H H C OH HO C H
CH2OH CH2OH
H C OH H C OH
these two aldotetroses are enantiomers.
They are stereoisomers that are mirror CH2OH CH2OH
images of each other
these two aldohexoses are C-4 epimers.
they differ only in the position of the
hydroxyl group on one asymmetric carbon
(carbon 4)

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 Properties
• Differences in structures of sugars are
responsible for variations in properties
• Physical
• Crystalline form; solubility; rotatory power
• Chemical
• Reactions (oxidations, reductions,
condensations)
• Physiological
• Nutritive value (human, bacterial);
sweetness; absorption 12
13
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 Structural representation of sugars

• Fischer projection: straight chain

representation
• Haworth projection: simple ring in
perspective
• Conformational representation: chair
and boat configurations

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 Rules for drawing Haworth projections

• draw either a six or 5-membered ring

including oxygen as one atom
O O

• most aldohexoses are six-membered

• aldotetroses, aldopentoses, ketohexoses are
5-membered

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 Rules for drawing Haworth projections

• next number the ring clockwise starting next to

the oxygen
5
O O
4 1 4 1

3 2 3 2

• if the substituent is to the right in the Fisher

projection, it will be drawn down in the Haworth
projection (Down-Right Rule)

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 Rules for drawing Haworth projections

• for D-sugars the highest numbered carbon

(furthest from the carbonyl) is drawn up. For
L-sugars, it is drawn down
• for D-sugars, the OH group at the anomeric
position is drawn down for a and up for b. For
L-sugars a is up and b is down

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D-glucose can cyclize in two
ways forming either furanose or
pyranose structures 19
D-ribose and other five-carbon
saccharides can form either
furanose or pyranose structures
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 Some important monosaccharides
• D-glyceraldehyde
• Simplest sugar
• Three carbon
• Aldotriose
• D-glucose
• Most important in diet
• An aldohexose sugar.
• Common names include
dextrose, grape sugar,
blood sugar.
• Most abundant organic
compound found in nature.
• D-galactose
• Milk sugar 21
 Some important monosaccharide

D-fructose
Fruit sugar
Also called fruit sugar.
A ketohexose.
Sweetest of all simple
sugars.
D-ribose
Used in RNA
A part of the backbone of
RNA.
When the C-2 OH is
removed, the sugar
becomes deoxyribose.
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 Cyclic Structure for Glucose
Glucose cyclic hemiacetal formed by reaction
of -CHO with -OH on C5.

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D-glucopyranose
Chair and boat conformations of a pyranose sugar

2 possible chair conformations

of b-D-glucose 24
Anomers - Mutarotation

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 Reactions of monosaccharides

• Normal chemical reactions related to the

presence of
–C=O in aldehyde and ketone groups
–OH groups

• Special reactions due to the large number of very

closely spaced functional groups in the molecule

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Reactions of carbohydrates
Epimerization
Enediol Rearrangement
Hemiacetal Formation
Reduction
Oxidation

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 Epimerization
In base, H on C2 may be removed to form enolate ion.

Reprotonation may change the stereochemistry of C2.

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 Enediol Rearrangement
In base, the position of the C=O can shift.
Chemists use acidic or neutral solutions of sugars to
preserve their identity.

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 Formation of Glycosides
• React the sugar with alcohol in acid.
• Since the open chain sugar is in equilibrium
with its a- and b-hemiacetal, both anomers
of the acetal are formed.
• Aglycone is the term used for the group
bonded to the anomeric carbon.

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 Ether Formation
Conversion of all -OH groups to -OR,
• Modified Williamson synthesis
• After converting sugar to acetal, stable in base.
• Helps to purify by recrystallization from water.

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 Ester Formation
Acetic anhydride with pyridine catalyst converts
all the free oxygens to acetate esters.

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 Reduction to Alditols
The carbonyl group of a monosaccharide can be
reduced to a hydroxyl group by a variety of
reducing agents, including NaBH4 and H2/M
CHO CH 2 OH
H OH H OH
HO H Ni HO H
H OH + H2 H OH
H OH H OH
CH2 OH CH 2 OH
D-Glucose D-Glucitol
(D-Sorbitol)

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 Reduction of Simple Sugars
• C=O of aldoses or ketoses can be reduced
to C-OH by NaBH4 or H2/Ni.

• Name the sugar alcohol by adding -itol to

the root name of the sugar.

• Reduction of D-glucose produces

D-glucitol, commonly called D-sorbitol.

• Reduction of D-fructose produces a mixture

of D-glucitol and D-mannitol.
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 Sugar alcohols are very useful intermediates

• Mannitol is used as an osmotic diuretic

• Glycerol is used as a humectant and can be nitrated
to nitroglycerin
• Sorbitol can be dehydrated to tetrahydropyrans and
tetrahydrofuran compounds (sorbitans)
• Sorbitans are converted to detergents known as
spans and tweens (used in emulsification
procedures)
• Sorbitol can also be dehydrated to 1,4,3,6-dianhydro-
D-sorbitol (isosorbide) which is nitrated to ISDN and
ISMN (both used in treatment of angina)

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Glycoside Formation:
An O-glycosidic bond can be formed between
two monosaccharides, when two -OH groups
react with each other. The product is called a
glycoside.
A glycosidic bond can link C1 of one carbohydrate
and C4 of the second carbohydrate.
CH 2 OH CH 2 OH

OH O H O OH
H H
H O OH H
OH
H H H

H OH H OH 36
 Glycoside Formation:
a or b -OH group on one cyclic monosaccharide
can form O-linkage with the one on another sugar.

• glycosidic bond CH2OH CH2OH

H O OH H O H
(oxygen bridge) H
OH H H
H
OH
OH H OH OH
H OH OH H

• sugar -O- sugar CH2OH

CH2OH H O H
H O H
H OH
H
OH H
o
OH
OH H OH H
H OH
+ H2 O 37
 Glycosidic Linkage
Two types of glycosidic bonds can be formed,
depending on the position of the C-1 OH (a or b
configuration)
Glycosidic bond
- linkage between a b C-1 OH and a a C-4 OH
is called b (1  4) linkage.

O
C1 O
a bonds b bonds
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 Lactose
• b-D-galactose joined to a-D-glucose via b (1,4)
linkage
• milk contains the a and b-anomers in a 2:3 ratio
• b-lactose is sweeter and more soluble than
ordinary a- lactose
• used in infant formulations, medium for penicillin
production and as a diluents' in pharmaceuticals

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 Lactose

• Milk sugar - dimer of b-D-galactose and

either a or b - D-glucose.
CH2 OH CH2 OH

OH O H O OH
H H
OH H O OH H
H H H

H OH H OH

b-D-galactose b-D-glucose

b (1 4) linkage, b-lactose
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For disaccharides, the sugar is either a or b
based on the form of the remaining C-1 OH.

CH2 OH CH2 OH

OH O H O OH
H H
OH H O OH H C1
H H H

H OH H OH

b-D-galactose b-D-glucose

b-lactose
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• Lactase
Enzyme required to
hydrolyze lactose.
• Lactose intolerance
• Lack or insufficient
amount of the enzyme.
• If lactase enters lower
GI, it can cause gas and
cramps.

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 Maltose
• 2-glucose molecules joined via a(1,4) linkage
• known as malt sugar
• produced by the partial hydrolysis of starch (either
salivary amylase or pancreatic amylase)
• used as a nutrient (malt extract; Hordeum vulgare);
as a sweetener and as a fermentative reagent

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 b-Maltose

• Malt sugar. Not common in nature except

in germinating grains.
CH2 OH CH2 OH

H O H H O OH
H H
OH H OH H
O H
OH
H OH H OH

a-D-glucose b-D-glucose

a-D-glucose and b-D-glucose, a (1 4) linkage.

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• It is called b-maltose because C-1 on b-D-
glucose is in the b position.

CH2 OH CH2 OH

H O H H O OH
H H
OH H OH H
O H
OH
H OH H OH

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• Uses for b-maltose:

• Ingredient in infant formulas.

• Production of beer.
• Flavoring - fresh baked aroma.

• It can be hydrolyzed by:

• maltose + H2O maltase 2 glucose

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 Sucrose
• a-D-glucopyranosido-b-D-fructofuranoside
• b-D-fructofuranosido-a-D-glucopyranoside
• also known as tablet sugar
• commercially obtained from sugar cane or sugar beet
• hydrolysis yield glucose and fructose (invert sugar) (
sucrose: +66.5o ; glucose +52.5o; fructose –92o)
• used pharmaceutically to make syrups, troches

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 Sucrose
CH2OH

H O H
• Disaccharide of H
a-glucose and OH H
b-fructose. OH
H OH
O
An unique linkage:
CH2OH O

a (1 2) linkage H OH
H CH2OH
OH H
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 CH2OH

H O H
This is a special case: H
OH H
The linkage between the
OH
glucose and fructose is
H OH
between two carbonyl O
carbons.
CH2OH O

H OH
H CH2OH
OH H

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 Oligosaccharides
• Trisaccharide: raffinose (glucose, galactose
and fructose)
• Tetrasaccharide: stachyose (2 galactoses,
glucose and fructose)
• Pentasaccharide: verbascose (3 galactoses,
glucose and fructose)
• Hexasaccharide: ajugose (4 galactoses, glucose
and fructose)

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Honey also contains glucose and fructose along with
some volatile oils
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 Structures of some oligosaccharides

Cycloheptaamylose ( a breakdown product of starch useful in

chromatographic separations)
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Structures of some oligosaccharides

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 Structures of some oligosaccharides

An enzymatic product (Beano) can be used to prevent

the flatulence 54
 Polysaccharides or glycans
• homoglycans (starch, cellulose, glycogen, inulin)
• heteroglycans (gums, mucopolysaccharides)
• characteristics:
• polymers (MW from 200,000)
• White and amorphous products (glassy)
• not sweet
• not reducing; do not give the typical aldose or ketose reactions)
• form colloidal solutions or suspensions

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 Starch
• most common storage polysaccharide in
plants
• composed of 10 – 30% a-amylose and 70-
90% amylopectin depending on the source
• the chains are of varying length, having
molecular weights from several thousands to
half a million

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Amylose and amylopectin are the 2 forms of starch. Amylopectin
is a highly branched structure, with branches occurring every 12
to 30 residues 57
(in starch)

(in cellulose)

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 Cellulose
• Polymer of b-D-glucose attached by b(1,4) linkages
• Yields glucose upon complete hydrolysis
• Partial hydrolysis yields cellobiose
• Most abundant of all carbohydrates
• Cotton flax: 97-99% cellulose
• Wood: ~ 50% cellulose
• Gives no color with iodine
• Held together with lignin in woody plant tissues

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Linear structures of cellulose and chitin
(2 most abundant polysaccharides)

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 Glycogen
• also known as animal starch
• stored in muscle and liver
• present in cells as granules (high MW)
• contains both a(1,4) links and a(1,6) branches at
every 8 to 12 glucose unit
• complete hydrolysis yields glucose
• glycogen and iodine gives a red-violet color
• hydrolyzed by both a and b-amylases and by
glycogen phosphorylase

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 Inulin
• b-(1,2) linked fructofuranoses
• linear only; no branching
• lower molecular weight than starch Jerusalem artichokes
• colors yellow with iodine
• hydrolysis yields fructose
• sources include onions, garlic, dandelions and
jerusalem artichokes
• used as diagnostic agent for the evaluation of
glomerular filtration rate (renal function test)

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 Chitin

• chitin is the second most abundant

carbohydrate polymer
• present in the cell wall of fungi and in the
exoskeletons of crustaceans, insects and
spiders
• chitin is used commercially in coatings
(extends the shelf life of fruits and meats)
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 Chitin
• Chitin is the second most
abundant carbohydrate
polymer
• Present in the cell wall of
fungi and in the
exoskeletons of
crustaceans, insects and
spiders
• Chitin is used commercially
in coatings (extends the
shelf life of fruits and
meats)

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 Dextrans

• products of the reaction of glucose and the enzyme

transglucosidase from Leuconostoc mesenteroides
• contains a (1,4), a (1,6) and a (1,3) linkages
• MW: 40,000; 70,000; 75,000
• used as plasma extenders (treatment of shock)
• also used as molecular sieves to separate proteins
and other large molecules (gel filtration
chromatography)
• components of dental plaques

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 Dextrins
• produced by the partial hydrolysis of starch
along with maltose and glucose
• dextrins are often referred to as either
amylodextrins, erythrodextrins or
achrodextrins
• used as mucilages (glues)
• also used in infant formulas (prevent the
curdling of milk in baby’s stomach)

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 Pectins
• pectins are heteropolysaccharides found in
the pulp of fruits (citrus, apples)
• on hydrolysis pectins yield galacturonic acid,
galactose, arabinose, methanol and acetic acid
• pectins are composed of galactans and
arabans
• used as gelling agents (to make jellies)

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 Gums
• widely used in the food and pharmaceutical industry
• used as: suspending agents, gelling agents,
thickening agents, emulsifiers, foam stabilizers,
crystallization inhibitors, adhesives, binding agents
• agar, tragacanth, karaya, carrageenan, guar gum,
gum arabic (acacia), furcellaran, sodium alginate,
locust bean gum

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