Carbohydrates Chemistry

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 Learning objectives
1. Define carbohydrate and the groups of saccharides
in chemical and descriptive terms
2. Relate the Fisher (open chain) and Haworth (ring)
structures of glucose and fructose
3. Understand the concepts of enantiomers,
diastereomers and epimers of simple sugars.
4. Know how the ring structures of aldehyde and
ketone sugars are formed
5. Describe the role that mutarotation plays in
intraconversion between the alpha and beta anomers.
 Learning objectives
6. Know the glycosidic bonds for the acetal and ketal bonds.
Know the different positions for the alpha and beta
linkage conformations.
7. Be able to convert the straight chain structure of any 5 or
carbon containing monosaccharide to its corresponding
ring structure
8.Tell the difference between the major sugar polymers in
biochemistry
9. Know the differences between glycoprotein and
proteoglycans.
10. Know the biochemical functions and differences between
the various heteropolysaccharides

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 Carbohydrates
Carbohydrates:
 a polyhydroxy aldehyde or

ketone
substancesthat yield such
compounds on hydrolysis
 Many, but not all, CHO
have the empirical formula

some also contain N, P,

or S
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 Carbohydrates
The O and H are present as in water
(H2O) hence the term “hydrate”
also called saccharides, which means
“sugars.”
 most abundant molecules on earth.
 Most are produce by photosynthesis

Photosynthesis
6CO2 + 6H2O + Energy C6H12O6 + 6O2
Respiration

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 Carbohydrates: Functions
 To yield energy (ATP)
 To maintain normal body temperature.
 Are linked to proteins and lipids to form key
intermediates and regulators
 To supply indigestible fibrous material to aid
digestion
 Important in the structure of nucleic acids &
metabolic precursors of all other biomolecules
 Energy-storage molecules (i.e. glycogen, starch).
 Structural - cell walls and exoskeletons
 Carbohydrate derivatives found in coenzymes
(FAD) and nucleic acids.
 lubricate skeletal joints and participate in
recognition and adhesion between cells
 Types of Carbohydrates

Carbohydrate

Mono Oligo Poly

Glyconoconjugates
saccharide saccharide saccharide

Glucose, fructose disaccharides cellulose, chitin, glycoproteins

Ribose (aldopentose) Glycoproteins starch, glycogen, and
Deoxy ribose (bacterial cell walls glucoaminoglycans proteoglycans

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 Monosaccharide
 Classified by their number of carbon atoms

Name Formula
triose C 3 H6 O 3
tetrose C 4 H8 O 4
pentose C 5 H1 0 O5
hexose C 6 H1 2 O6
heptose C 7 H1 4 O7
octose C 8 H1 6 O8

 Two types of monosaccharide structures:

 Aldoses
 Ketoses
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 Aldoses

O
Aldoses are
║
monosaccharides
C─H aldose
• with an aldehyde group │
• with many hydroxyl (-OH) H─ C─OH
groups. │
triose (3C atoms) H─ C─OH
│
tetrose (4C atoms)
CH2OH
pentose (5 C atoms)
hexose (6 C atoms) Erythose, an
aldotetrose

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 D-Aldoses
(pentose)
(triose) (tetrose)

( stereoisomers of the
hexoses)

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 Ketoses
CH2OH
Ketoses are
│
monosaccharides
C=O ketose
• with a ketone group │
• with many hydroxyl (- H─ C─OH
OH) groups. │
H─ C─OH
│
H─C─OH
│
CH2OH
Fructose, a ketohexose

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 D-ketoses

Note:
Ketoses have
one fewer
asymmetric
center than do
aldoses with
the same
number of
carbons

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 stereoisomers
 Asymmetric C - carbon atoms
attached to four different atoms
or groups
 All the monosaccharide except
DHA
- contain one or more
asymmetric (chiral) C atoms
and
-thus occur in OA forms.
 Glyceraldehyde contain one chiral
center and therefore has two
different optical isomers or
enantiomers.
 A molecules with n chiral center
can have 2n stereoisomers .
How many stereoisomers does an
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aldohexose contain ? 16
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 The orientation of- OH and-
H groups around the carbon
atom adjacent to the
terminal primary alcohol
carbon determines its D
or L form .
 The - OH group
on the right, the
sugar is the D series
on the left, it is the L-
series.
 These D and L configuration
are also called Enantiomers
 Optical Activity
 The presence of asymmetric carbon atom causes optical
activity.
 When a beam of plane polarized light solution of CHO

– It rotate the light either to right or to left.

 Molecules are called dextrorotatory (+) (d) or
levorotatory (-)(l).
 Thus, D- glucose - dextrorotatory but
 D- fructose - levorotatory.
 When equal amounts of D and L isomers are present, the
resulting mixture has
• no optical activity
• Such a mixture is called racemic or DL mixture.
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Optical Activity
Epimers: two sugars that differ only in the
configuration around one carbon atom

D-glucose and two of its epimers

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 Anomerism
Only aldoses or ketose having
– five or more carbon atoms can form pyranose and
furanose rings
Formation of hemiacetal or hemiketal ring
result in the creation of an anomeric carbon at
 carbon 1 of an aldose
 carbon 2 of Ketose

In solution as interamolecular hemiacetal or

hemiketal exist as α
and configuration
The alpha anomer: Where- OH group is down o
The beta anomer:Where- OH group is up
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Anomerism:
 differ in their
configuration
about either
hemiacetal or
hemiketal
carbon atom
 Create an
asymmetric center

C-1: anomeric
carbon atom
mutarotation

Anomers
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(two cyclic forms of D-glucose) 23
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 The four aldotetroses
• Enantiomers: stereoisomers that are mirror images
– example: D-erythrose and L-erythrose are
enantiomers
• Diastereomers: stereoisomers that are not mirror
images
– example: D-erythrose and D-threose are
diastereomers
Mirror Mirror
plane plane

CHO CHO CHO CHO

H OH HO H HO H H OH
H OH HO H H OH HO H
CH2 OH CH2 OH CH2 OH CH2 OH
D-Erythrose L-Erythrose D-Threose L-Threose

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 Disaccharides

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 Disaccharides
 Contain two monosaccharide unit joined by
glycosidic bonds via a condensation
reaction
 The anomeric hydroxyl group and a
hydroxyl group of another sugar form a
glycosidic bond
1.maltose “malt sugar”- two glucose units
(alpha)
2.cellobiose- two glucose units (beta)
3.lactose “milk sugar”- galactose & glucose
4.sucrose “table sugar”- glucose & fructose
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 Maltose or malt sugar
 -obtained from hydrolysis of starch
 -consists of α-D-glucose and α -D-glucose
 -has an α-1,4-glycosidic bond
 -Also named as [α-D-Glucopyranosyl-
(1,4)-α-D-Glucopyranose ]

Free α-OH

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 Lactose
– about 5% - 8% in human milk, 4% -
5% in cow’s milk
– β ,D-galactose and β, D-glucose joined
by a β -1,4-glycosidic bond
– Also called β-D-Galactopyranosyl-(1,4)-
β-D-Glucopyranose

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 Sucrose or table sugar
• - is obtained from sugar cane and sugar beets.
• - consists of α-D-glucose and β-D-fructose.
• - has an α,β-1,2-glycosidic bond
• - Also named as [α-D-Glucopyranosyl-(1,2)-β-D-Frictofuranoside ]

α-D-glucose

β -D-fructose

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Reducing vs. non -reducing sugars
 If the carbonyl linkage involves the
carbonyl groups of both sugars
 as in sucrose
 the resulting disaccharide – non-
reducing sugars
 On the other hand if the glyconyl linkage
involves the carbonyl group of only one
of the 2 sugars
 as in maltose and lactose
the resulting disaccride is reducing

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Monosaccharides are Reducing Agents
• Monosaccharides can be oxidized by relatively
mild oxidizing agents
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–such as ferric (Fe3+) or cupric (Cu2+) ion

• The carbonyl carbon is oxidized to a carboxyl
group
• Glucose and other sugars capable of reducing
ferric or cupric ion are called reducing sugars

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 All monosaccharides and
1 Some common disaccharides
are reducing sugars
Maltose
[α-D-Glucopyranosyl-(1,4)-α-D-Glucopyranose ] Reducing sugar !
Contains free
anomeric carbon
atom

 Nonreducing sugar !
Contains no free
anomeric carbon atom
 nonreducing
disaccharides
are named as
glycosides
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 OLIGOSACCHARIDE SUGARS
 small polymers (2-9 suger residues )often found
attached to polypeptides in glycoproteins and some
glycolipids.
attached to membrane and secretory proteins found
in endoplasmic reticulum and Golgi complex of
various cells
Two classes: N-linked and O-linked
The N-linked oligosaccharides
 have a minimum of 5 sugar residues
 attached to polypeptides by an N-glycosidic bond
with a chain amide group of amino acid,
asparagine
O-linked oligosaccharides
 generally short (1-4 sugar residues)
 attached to polypeptides by the side chain OH
group of amino acids serine or threonine or
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OH group of membrane lipids 35
Polysaccharides
 The large macromolecules formed from
simple sugar
Many animals store excess sugar in a
polysaccharide called glycogen
The glycogen stored in
•Muscles supplies the energy for
muscle contraction and thus, for
movement.
• liver regulate glucose
homeostasis in blood
Plants store excess sugar polysaccharide
called plant starch
 Polysaccrides cont.
more than 10 units
classification:
Polysaccharide
: carbohydrates
1. • homopolysaccharides
One type of units
that yield a large
Glc - starch, glycogen, cellulose
number of
Gal - agar
molecules of
Fru - inulin
monosaccharide
(﹥10). 2. • heteropolysaccharides
More types of units

• linear
• branched
• interlinked

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 Polysaccrides cont.
Differences between homopolysaccharides
and heteropolysaccharides

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 Polysaccrides cont.
homopolysaccharides of glucose

starch
amylose - nonbranched  (1-4 )
amylopectin - branched  (1-4 ) +  (1-6 )
glycogen - branched  (1-4 ) +  (1-6 )
cellulose - nonbranched  (1-4 )

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Chloroplast Starch granules
Polysaccrides cont .

Amylose
(a) Starch: 1 m
a plant polysaccharide
Amylopectin
Mitochondria Glycogen granules

Glycogen
(b) Glycogen: 0.5 m
an animal polysaccharide
 Cellulose
 -is a polysaccharide of glucose
units in unbranched chains.
 -has β-1,4-glycosidic bonds.
 -cannot be digested by humans
because humans cannot break
down β-1,4-glycosidic bonds.
 -Lack of cellulase enzymes

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 Polysaccrides cont.
CHO O
H N H-CCH3
HO H
HO H
H OH
CH2 OH
N-Acetyl-D-glucosamine

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 Polysaccrides cont.
 inulin fru - fru  ( 1- 2 )
storage polysaccharide in tubers and roots of
plants - garlic, onion, dahlias, artichokes,
dandelions

 agar gal -gal  ( 1- 4 ) &  ( 1- 3

)
gelling agent - food, culture media, imprinting
materials
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 Heteropolysaccharides
Most important GLYCOSAMINOGLYCANS
Common structure: A
N-acetylhexosamine
(glucosamine, galactosamine)
uronic acid
(gluccouronic, iduronic) B

A B A B A

 ( 1- 3 )  ( 1- 4 )  ( 1- 3 )  ( 1- 4 )  ( 1- 3 )  ( 1- 4 )
Always in complex with proteins - proteoglycans
Part of inercellular matrix (bone, cartilage, ligament)

1.Hyaluronic acid -N-acetylglucosamine + glucuronic a.

2. Chondroitin sulfate - N-acetylgalactosaminesulphate + glucuronica.
3.Dermatansulphate- N-acetylgalactosaminesulphate + iduronic a.
4. Heparin – glucosaminesulphate+ D-gluccouronic A. OR L-iduronic
A.(bothsulphated) 45
 Function of GAGS
1.They have the special ability to bind
large amounts of water
2. Since they are negatively
charged ,they attract and tightly bind
cations like ca++,they also take-up Na+
and K+

3. GAGs helping maintain the water

and salt balance of the body.

4. GAGs’ play an important role in

mediating cell-cell interactions
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 Polysaccrides cont.
 Glycosaminoglycans:
heparin: natural anticoagulant
hyaluronic acid: a component of the
vitreous humor of the eye and the
lubricating fluid of joints
chondroitin sulfate and keratan
sulfate: components of connective
tissue

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 GLYCOCONJUGATES
Glycoproteins
 proteins to which oligosaccharides are covalently
attached
The glycoprotein carbohydrate chains are often
branched instead of linear
For example:
- Glycophorin- found in human red cell membrane
- Human gastric glycoprotein (mucin).
-Many protein hormones, receptors
Proteoglycan
When GAGs are attached to a protein
molecules
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 SUMMARY OF THE CHEMISTRY OF CARBOHYDRATES

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