Carbohydrates

Carbohydrates
Hydrates of Carbon: formula is Cm(H2O)n
• Saccharides: Latin: saccharum = sweet
• Monosaccharides : 1 unit (e.g. glucose or fructose)
• Disaccharides: 2 sugar units (residues)
• Oligosaccharides: 3 -10 sugar residues (units)
• Polysaccharides: long chains up to 100s - 1000s
• Monosaccharides: Triose, tetrose, pentose, hexose refers
to number of carbons in the sugar structure (unit).
Carbohydrates are involved in:
1. Energy transport and storage.
2. Structural e.g. bacterial cell walls, cellulose
3. Information e.g. signals on proteins and membranes.
Carbohydrates
• The two major carbohydrate families:
CH2OH
H O
C C O
(H C OH)n (H C OH)m
CH2OH CH2OH
Aldose (n = 1 - 4) Ketose (m = 0 - 3)
• The aldoses derive from D-glyceraldehyde,
the ketoses from dihydroxyacetone:
Dihydroxyacetone
H O
CH2HOH O
C CH2OH
C O C
H C OH C O
CHH OHC OH
CH2OH 2
D-glyceraldehyde CH2OH
CH2OH
Carbohydrates
Except for dihydroxyacetone, all the aldoses and ketoses
have asymmetric (chiral) carbons.

Some common abbreviations

Glucose Glc
Glucosamine GlcN
Fructose Fru
Galactose Gal
Galactosamine GalN
N-Acetylglucosamine GlcNac
Ribose Rib
 Carbohydrates
• In nature, most sugars are D- while most AA are L-.
• D- and L-glyceraldehyde are reference molecules for
assignment of stereochemistry (absolute configuration).

CHO CHO CH
OH HO C H H C OH HO C
OH CH2OH CH2OH CH
ldehyde L -Glyceraldehyde D-Glyceraldehyde L -Glycer

These are non-superimposable mirror images, or enantiomers.

The diagrams, which use conventions to provide 3D information
(solid wedge: bond coming out of plane; dotted wedge: bond
going back into plane) are called “perspective formulas”.
Carbohydrates
• Fischer projection formulas retain the stereochemical
information but use lines for the bonds.
1
CH2OH CH2OH
2
C O O Why D-? The chiral C
3
HO C H HO furthest from the C=O
4
H C OH = OH has the same
5
configuration as D-
H C OH OH glyceraldehyde.
6
CH2OH CH2OH
D-Fructose
• Carbohydrates are optically active: they rotate the plane of monochromatic plane-
polarized light in opposite directions. dextrorotatory (+) or levorotatory (-).
Carbohydrates
Dihydroxyacetone X = 0 2X = 1
Aldohexoses X = 4 2X = 16
Ketohexoses X = 3 2X = 8

8 Aldohexoses + 8 enantiomers
4 Ketohexoses + 4 enantiomers
https://www.chemistrysteps.com/aldoses-and-ketoses-classification-and-stereochemistry
Carbohydrates
Cyclic Carbohydrates
In solution, many carbohydrates exist in a cyclic form.
This is because of a tendency of carbonyl groups to react
reversibly with alcohols:
H OH
R1 C + HO R2 R1 C OR2
O
H

Aldehyde + Alcohol Hemiacetal

R3 OH
R1 C + HO R2 R1 C OR2
O
R3
Ketone + Alcohol Hemiketal
Carbohydrates
Cyclic Carbohydrates
• Since each of the carbohydrates we have discussed
has both a carbonyl and one or more alcoholic
hydroxyls, an intramolecular hemiacetal or
hemiketal is possible, giving a cyclic structure.
• The main restriction is steric: small rings (4 or fewer
atoms in the ring) are unstable, so the stable rings
will be those containing 5 or 6 atoms (6-membered
are more stable than 5-membered).
• The reactions create one additional chiral center
• Formation of the cyclic forms is reversible
 Carbohydrates
Glucose can form two cyclic structures involving a 6-membered
ring. They are different because the new chiral centre (at C1) can be
created in two different ways: CH2OH
D-Glucose 5C
H O
H
C H C
1 CHO CH2OH
1 OH
OH OH H
OH H C OH
CH2OH
H 5 C C
a -D-

OH
C

C
HO C H H

H
HH C C 2O
OH
OH H 1 O H H OH
OH OH C
G

CC H H
C
l

H O
C C
C
u

hemiacetal
OH

5 OH OHH OH C H
c

OH a-D-Glucopyranose
H
O
o

H OH O C
CH2 OH
H
p

CH2OH CH C H OH O
yranose

CH H C CH2OH C
OH
H OH C
OH

O
C

C OH H
H

H
O

C H
These are called “Haworth” a-D-Glucopyranose
OH C
a -D
-G OH OH H H b-D
OH

diagrams – a method for showing luco CH

C

C
H

pyra H C 2 OHC
n
b-D-Gluc

the stereochemistry of the ose

OH

C
C H OH
H
C

O
OH

molecules in two dimensions. H

H

OH
C
CH2

Ob-D-Glucopyranose
H OH
o
Carbohydrates
• The 6-membered ring is preferred over the
less stable 5-membered ring. The structure is O
called a pyranose because of the ring pyran:

C1 is a new asymmetric C: Isomers that differ only at the

hemiacetal or hemiketal C are called anomers and the C
is the anomeric C.
• -anomer: OH on C1 is on the same side (cis) of
the ring as the C6.
• -anomer: OH on C1 is opposite (trans) to C6.
OH on asymmetric C on the “right” in the Fischer
diagrams are "down" in the Haworth Diagrams.
Carbohydrates
Fischer structures (non-cyclic) are correct for C3 or C4 sugars in
solution, otherwise ring structures are more stable. In water, all
three forms exist in equilibrium:

a Chain b
36% 0.01% 64%
The -anomer and -anomer can interconvert through the trace
amounts of the non-cyclic (‘linear’) form.
 Carbohydrates
• The interconversion is called mutarotation and can be
measured by the rotation of plane-polarized light.
a Chain b
36% 0.01% 64%
a
100o
1.Pure -D-Glc rotates light +112 o
2.Pure -D-Glc rotates +19o
q 3.At equilibrium the mixture rotates
light +53o (a weighted average of the
contributions from the two forms:
20o 0.36x(+112o) + 0.64x(+19o) = +53o
b
Time
Carbohydrates
D-ribose
• The pentoses also form H O
hemiacetals: C
H C OH
H C OH
H C OH
CH2OH

HOH2C O H HOH2C O OH

H H H H
OH
H H H

OH OH OH OH
a-D-ribose b-D-ribose
Carbohydrates
Cyclic Ketoses HOH2C OH
O
D-fructose can form a
C
furanose ring as a result of H HO
an intramolecular reaction CH2OH
H
between the carbonyl group
and the C5 hydroxyl group.
OH H

HOH2C O CH2OH HOH2C O OH

The 5-membered ring structures
are called Furanose structures
because of the resemblance to
furane: H HO H HO
OH
O H H CH2OH

OH H OH H

a- D-fructofuranose b-
Carbohydrates
Sugar Derivatives
1. Reduction of glyceraldehyde yields glycerol, an alcohol.
Reduction of glucose yields D-glucitol (Sorbitol, a sweetener):
D-Glucose

CH2OH
CHO CH2OH
H C
OH OH
OH H
HO H C HO H C
OH OH H O
OH OH
OH C OH C

CH2OH CH2OH OH
H
Glucitol (Sorbitol)
 Carbohydrates
Sugar Derivatives
2. Monosaccharides are reducing agents.
• They give up electrons and are themselves oxidized. Oxidation of
aldols yields the Aldonic acid family (aldehyde oxidized to a carboxyl
group). This can be detected in an alkaline solution of Copper.
D-Glucose

• Cu+ is insoluble and

-
O CHO OH
CHO 2
precipitates from solution. C
OH H C O
• Only linear sugars are OH
HO D-Glc C HO H
reactive.
OH H
• Ketoses react slowly OH +2 +OH OH
2 Cu 2 Cu
because they must OH C C
OH
isomerize to the aldehyde. CH OH HCH OH O
2 2

D-Gluconate
Carbohydrates
Sugar Derivatives
3. Sugar phosphate esters are intermediates in sugar synthesis that
prevent transport of the sugar across membranes.

CH2OH
Remember: Glucose, a O
small uncharged
molecule, can pass CH2 P
OH
through the cell O OH P
membrane!
The phosphorylation OH
OH
adds a charged OH OH Glc-1-P
phosphate group so the
glucose 6-phosphate OH
(Glc-6-P) cannot easily O
cross the cell Glc-6-P -
P = O P O
membrane. -
O
Carbohydrates
Sugar Derivatives
4. Amino Sugars
CH2OH CH2OH
(Note that Glc and Gal are
O O
HO epimers at C4.)

OH OH
OH OH OH

NH2 NH2

a -D-glucosamine a -D-galactosamine
CH2OH
O
5. Sugar amides
OH
OH OH

N C CH3
H O
N-acetyl-glucosamine (GlcNAc)
Carbohydrates
Sugar Derivatives
6. Deoxy-sugars

HOH2C O H HOH2C O H

H H H H
H OH H OH

OH OH OH H
a -D-ribose a -D-2-deoxyribose

2-deoxyribose is the sugar component of

deoxyribonucleic acid (DNA).
 Carbohydrates
Disaccharides CH2OH CH2OH

O O
OH
• Maltose a
b
OH
A reducing sugar OH
OH
OH OH

made from starch OH OH

by amylase.
Acetal
CH2OH CH2OH
O O
OH

OH OH
OH O

OH OH

Hemiacetal
(-D-glucopyranosyl-(1→4) -D-glucopyranose)
= Maltose = Glc (1→4) Glc

https://proteopedia.org/wiki/index.php/Alpha-Amylase
Carbohydrates
Acetal
Disaccharides CH2OH CH2OH
O O
OH

OH OH
OH O

OH OH

Hemiacetal
Notes:
1. The glucose on the left is an acetal. It is non-
reducing and non-mutatrotating.
2. The glucose on the right is a hemiacetal. It has a
reducing end and mutarotates.
3. Glycosidic bonds join sugars (or sugars to another
group, e.g. amino acid side chains of proteins).
Carbohydrates
Disaccharides CH2OH
O

OH
OH O
OH CH2
O

Iso-maltose (Glc (1→6) Glc) is OH

OH OH
a reducing sugar made from
hydrolysis of dextrans. OH
Carbohydrates
Disaccharides

Lactose Gal (1→4) Glc

(remember, Glc and Gal are epimers at C4) is a reducing sugar. The major sugar of
milk.

β-galactosidase cuts this glycosidic bond

Carbohydrates
Disaccharides CH2OH
O
Sucrose: Glc (1→2) Fru
Fru (2→) Glc a
1
A non-reducing sugar made by OH
plants (table sugar). Sucrose is an OH
example of a disaccharide formed
by reacting the anomeric carbons OH O
with each other. O
HOH2C
Therefore, sucrose is non-reducing
and does not undergo 2 b
mutarotation. H HO
H CH2OH

OH H
Carbohydrates
Polysaccharides
Very long chains of sugar units are called polysaccharides.
The units are linked by the same kinds of glycosidic bonds
(often (1→4) or (1→4)).
The chains can be straight or branched.
Polysaccharides play two roles in biology:
1. Storage of sugar units (compact, units can be easily added
or removed by enzymes according to need)
2. Structural (tough molecules, resistant to degradation by
enzymes, fold up into organized structures to maintain cell
walls)
 Carbohydrates
Starch is the storage form of D-Glc in plants. Two types:
1. Amylose: Unbranched chains of (1→4) linked Glc
units, up to 4,000 per chain. Forms a helix

Wiki

2. Amylopectin: up to 200 amylose

chains linked by (1→6) branches.
Cannot form a helix.
a -1,4
a -1,6

…at intervals of 24 to 30 glucose subunits

Carbohydrates
Glycogen: Animal cell storage of Glc (liver and skeletal muscle). Similar to
amylopectin, but more branched. ~15-30 sugars per branch.

Alpha-linked glucose polymers (starch, glycogen) are found in all organisms, which use
them to store glucose.
Some plant seeds (the cereal grains) contain large amounts of glucose, stored as starch for
the use of the germinating seed.
-linked polymers are easy to digest, so they are a valuable source of food for many
animals. Digestive enzymes called amylases hydrolyze the glycosidic bonds, releasing the
sugar units.
Carbohydrates
Structural polysaccharides
1) Cellulose: (Glc (1→4) Glc)n
• Linear chain of 10 - 15,000 glucose units. This is a strong rod-like structure of
parallel chains packed side-by-side.
• the fibrous structure of cellulose is useful for textiles (cotton, linen), industrial
fibre (hemp, sisal) and paper. Cellulose comprises much of the mass of wood!

• Cannot be digested by humans, but cattle and

other ruminants have an extra stomach
(rumen) teaming with bacteria and protists
that secrete cellulase, an enzyme that cleaves
β1➔4 glycosidic bonds to release glucose.
Carbohydrates
Structural polysaccharides
2) Peptidoglycan
• Exclusive to bacteria
(Peptidoglycan is a polysaccharide
found in many bacterial cell walls)
• Alternating β-1,4-linked N-
acetylglucosamine (GlcNAc) and
N-acetylmuramic acid (MurNAc)
sugars that are cross-linked by
short peptides
• Forms a three-dimensional mesh-
like cell wall structure that
provides rigidity to the bacteria and
protects it from osmotic stress
 Carbohydrates Sugar linkages to proteins:

Oligosaccharides
The bond types that link sugar
units together in disaccharides
can be used in sugar
compounds of any length.
• Since any hydroxyl group on a
sugar unit can react with the
anomeric carbon of another unit
to form a glycosidic bond,
branching structures are possible.
• Among the most important
oligosaccharides (~15 sugar
units) are those that are attached
to proteins or lipids on the
outside of various animal cells.