Lecture 8

Carbohydrates
 Carbohydrates
• Most abundant class of biological
molecules on Earth
• Originally produced through CO2
fixation during photosynthesis
 Roles of Carbohydrates
• Energy storage (glycogen, starch)
• Structural components (cellulose, chitin)
• Cellular recognition
• Carbohydrate derivatives include DNA,
RNA, co-factors, glycoproteins, glycolipids.
 Carbohydrates
• Monosaccharides (simple sugars) cannot
be broken down into simpler sugars
under mild conditions
• Oligosaccharides = "a few" - usually 2 to
10
• Polysaccharides are polymers of the
simple sugars
 Monosacharides
(C•H2O)n where n ≥3
• Triose (3 C)
• Tetrose (4 C)
• Pentose (5 C)
• Hexose (6 C)
• Heptose (7 C)
• Octose (8 C)
 Monosaccharides
• Polyhydroxy ketones (ketoses) and
O
aldehydes (aldoses) H
C CH2OH
• Aldoses and ketoses contain
H C* OH C O
aldehyde and ketone functions,
respectively HO C* H HO C* H

• Ketose named for “equivalent H C* OH H C* OH

aldose” + “ul” inserted CH2OH CH2OH

D-ribose D-ribulose
• Empirical formula = (CH2O)n
 Monosaccharides are chiral
• Aldoses with 3C or more and
ketoses with 4C or more are chiral
• The number of chiral carbons
present in a ketose is always one
less than the number found in the
same length aldose O
H
• Number of possible steroisomers = C CH2OH
2n (n = the number of chiral H C* OH C O
carbons)
HO C* H HO C* H

H C* OH H C* OH

H C* OH H C* OH

CH2OH CH2OH
D-glucose D-fructose
 Stereochemistry
Enantiomers Diastereomers Epimers
O O O O O O
H H H H H H
C C C C C C

HO C* H H C* OH HO C* H H C* OH H C* OH HO C* H

H C* OH HO C* H HO C* H HO C* H HO C* H HO C* H

HO C* H H C* OH H C* OH HO C* H H C* OH H C* OH

HO C* H H C* OH H C* OH H C* OH H C* OH H C* OH

CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH

L-glucose D-glucose D-mannose D-galactose D-glucose D-mannose

•Enantiomers = mirror images

•Pairs of isomers that have opposite configurations at one or
more chiral centers but are NOT mirror images are
diastereomers
•Epimers = Two sugars that differ in configuration at only one
chiral center
 Cyclization of aldose and ketoses
introduces additional chiral center
• Aldose sugars (glucose) can cyclize to form a cyclic hemiacetal
H H
ALDEHYDE NEW CHIRAL
O O CARBON

C H C* R1
H R1
O
R2
ALCOHOL O
H R2 HEMIACETAL

• Ketose sugars (fructose) can cyclize to form a cyclic hemiketal

H H
KETONE NEW CHIRAL
O O CARBON

C R C* R1
R R1
O
R2
ALCOHOL O
H R2 HEMIKETAL
Cyclization of aldose and ketoses
 Haworth Projections
O
In D configuration
H
C1 -OH up = beta
-OH down = alpha
H C2 OH 6
HO C3 H 5
H C4 OH 4 1
H C5 OH 2
3 Anomeric carbon
CH2OH
(most oxidized)

For all non-anomeric carbons, -OH groups point

down in Haworth projections if pointing right in
Fischer projections
Monosaccharides can cyclize to form
Pyranose / Furanose forms
α = 64% α = 21.5%
β = 36% β = 58.5%

α = 13.5%
β = 6.5%
Isomeric forms of fructose
 Conformation of Monosaccharides

Pyranose sugars not planar molecules, prefer to be in either of

the two chair conformations.
 Derivatives of
Monosaccharides
 Sugar Phosphates

Metabolized as
phosphate esters
 Deoxy Sugers
Hydrogen atoms replaces -OH group on C-2.
Important to structure of nucleic acids.
 Amino Sugars
Amino group (NH-) substituted for -OH
group in monosaccharide.
CH2OH

OH O OH
OH H

H H

H NH

C O

CH3

ß-D-N-acetyl glucosamine
 Sugar alcohols

Replace carbonyl
oxygen to form
polyhydroxy
alcohols
Glyceraldehyde
glycerol
-ose  -itol.
Ribose  ribitol
 Sugar acids
Oxidation of carbonyl group
generate aldonic acids while
C-6 oxidation results in uronic
acids.
glucose  gluconate or
glucuronate D-gluconate cyclizes to D-glucono-δ-lactone

β-D-glucuronate
 Ascorbic acid

Derived from D-glucuronate.

• Esential cofactor for enzymesthat
catalyze the hydroxylation of
proline and lysine
• Primates cannot do the
conversion, so must be supplied
in the diet.
Monosaccharide structures you
need to know
• Glucose
• Galactose
• Fructose
• Ribulose
• Glyceraldehyde
• Dihydroxyacetone
 Carbohydrates
• Monosaccharides (simple sugars) cannot be
broken down into simpler sugars under mild
conditions
• Oligosaccharides = "a few" - usually 2 to 10
• Polysaccharides are polymers of the simple
sugars
 Glycosides

• Glycoside: a carbohydrate in which the -OH of the

anomeric carbon is replaced by -OR
• those derived from furanoses are furanosides; those
derived from pyranoses are pyranosides
• Glycosidic bondthe bond from the anomeric carbon
to the -OR group:
 CH2OH CH2OH

O hemiacetal
O OH
Glycosidic Linkage OH OH
OH
OH OH
OH OH
alcohol

Hydrolysis
H 2O
H 2O
Condensation

CH2OH CH2OH
acetal
O O OH
OH OH
O
OH

OH OH
glycosidic linkage
 CH2OH CH2OH
Disaccharides
CH2OH
H OH maltose cellobiose
O H H O H O OH
CH2OH
OH H OH H OH H
O H O O
OH H
OH H H
H OH H OH H OH
OH H
(α-D-glucosyl-(1->4)-β-D-glucopyranose)
H OH

CH2OH (β-D-glucosyl-(1->4)-β-D-glucopyranose)
H O H CH2OH
OH H lactose H O OH
CH2OH
OH OH H
OH O
H OH sucrose OH H
O
H
O
CH2OH H OH
O H H
H OH
H OH
H CH2OH (β-D-galactosyl-(1->4)-β-D-glucopyranose)
OH H
(α-D-glucosyl-(1->2)-β-D-fructofuranose)
 Reducing and nonreducing sugars
• carbonyl group or anomeric carbon are the most
oxidizable site in monosaccharides and most
disaccharides, therefore they are reducing sugers
(glucose, maltose, cellobiose, lactose)
• Detected by the ability to reduce Cu2+ --> Cu+ with
Benedict’s reagent (blue --> red-orange insoluble
products ).
• Non-reducing sugars have both anomeric carbons in
a glycosidic bond (e.g. sucrose).
 Aglycones
• Aglycones: an organic molecule, such as alcohol,
amines or thiols, that forms a glycosidic linkage
with the anomeric carbon of the sugar to form
glycoside. The most common encountered
glycosides other than oligosacharides are the
nucleosides or called N-glycosides.

guanosine
(β-D-ribofuranosylguanine) Adenosine