Carbohydrates

Can you live without sugar?

•  Soda/Punch
•  Cookies
•  Candy
•  Chocolate
•  Desserts
•  Sugary
Cereals
•  Ice cream
Ø  60% of our food
should come from
carbohydrates.
 CARBOHYDRATES
Ø The most abundant organic molecules in nature.
I. Functions:
• Provide a significant fraction of the energy in the diet of most
organisms
•  Important source of energy for cells
•  Can act as a storage form of energy
•  Can be structural components of many organisms
•  Components  of  several  metabolic    pathways
•  Can be cell-membrane components mediating intercellular
communication
•  Can be cell-surface antigens
•  Can be associated with proteins and lipids
•  Part of RNA and DNA
•  Recogni8on  of  cellular  phenomena,  such  as  cell  recogni8on  and  
binding  (e.g.,  by  other  cells,  hormones,  and  viruses)  
Carbohydrates -are polyhydroxyaldehydes,
polyhydroxyketones, or compounds that yield
them after hydrolysis.
Ø  are hydrates of carbon.

General Molecular Formula: Cn (H2O)m

§  Glucose (blood sugar): C6H12O6 written as C6(H2O)6

§  Sucrose (table sugar): C12H22O11 written as C12(H2O)11
 II.  Classifica+on  of  carbohydrates  
Ø  CHO’s  that  have  a  free  carbonyl  group  have  the  suffix  “-­‐ose.”
Note:  ketoses  (with  some  excep8ons  e.g.,  fructose)  have  an  
addi8onal  2  leGers  in  their  suffix;  ”-­‐ulose”,  e.g.,  xylulose  

w  Monosaccharides - simple sugars with multiple OH groups.

Ø  Based on number of carbons (3, 4, 5, 6), a monosaccharide.
is a triose, tetrose, pentose or hexose.
w  Disaccharides - contain 2 monosaccharides covalently linked.
w  Oligosaccharides - a few monosaccharides covalently linked.
- contain from 3 to about 12 monosaccharide units.
w  Polysaccharides - polymers consisting of chains of monosaccharide
or disaccharide units.
§  contain > 12 monosacch units, can be 100s of sugar units.
 Classification of Carbohydrates
based on number of sugar units in total chain

Carbohydrate

Monosaccharide Oligosaccharide Polysaccharide Glycoconjugates

§  Glucose, fructose §  Disaccharides §  Cellulose, chitin, §  Glycoproteins and
Ribose (aldopentose) Glycoproteins starch, glycogen, proteoglycans
Deoxy ribose (bacterial cell walls) glucoaminoglycans
 Nomenclature of
Monosaccharides

Carbohydrate nomenclature is unique

to “sugar chemistry” ---
monosaccharides are not named using
the IUPAC rules.
Monosaccharides names end in “ose”
Monosaccharides can be classified by the:
Carbonyl group
Number of carbons
Both
 Classification of Monosaccharides based on
location of the carbonyl group C=O
Aldose- a monosaccharide containing an aldehyde group.
Ketose – a monosaccharide containing a ketone group.

Figure 7.2. Examples of an aldose (A) and a ketose (B) sugar.

Monosaccharide Classification based on number of
carbons in the chain

Figure 7.1. Examples of monosaccharides found in

humans.
Monosaccharides

Simple sugar and serves as the building block of larger

molecules.
With molecular formulas that are usually multiples of CH2O
Configurational Relationships among the Isomeric D-
Aldotetroses, D-Aldopentoses, and D-Aldohexoses
 Fischer Projections

•  Purpose of Fischer projections is to show configuration at

stereogenic center without necessity of drawing wedges
and dashes or using models (3D).

•  Use Fischer Projections

- represent three-dimensional structures of stereoisomers
on a flat page
•  With this system, a tetrahedral carbon atom is
represented by two crossed lines.
 1

4 3

2
Fischer Projection Formula
Fischer Projections
horizontal line is coming vertical line is going back
out of the plane of the behind the plane of the
page (toward you) paper (away from you)

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

CHO CHO
CHO
HO H HO H
HO C
CH2OH CH2OH CH2OH
H
Monosaccharide Classification based on
STEREOCHEMISTRY

Stereochemistry
•  Study of the spatial arrangement of molecules.
Isomers
•  molecules that have the same molecular formula, but
have a different arrangement of the atoms in space.
Stereoisomers
•  Stereoisomers are distinct molecules with the same
sequence of bonded atoms but a different orientation
of these atoms in space/different spatial
arrangements.
 ISOMERISM
Structural isomers
Compounds with the same molecular formula but with
different structures

Functional group isomers

with different functional groups
E.g. glyceraldehyde and dihydroxyacetone

Positional isomers
with substituent groups on different C-atoms
E.g.

COO--CHOPO3--CH2OH and COO--CHOH-CH2OPO3-

2-Phosphoglycerate 3-Phosphoglycerate
 STEREOCHEMISTRY

Ø  Due to the fact that carbohydrates contain multiple

stereocenters, many isomers are possible:
Enantiomers
Epimers

Enantiomers- A special type of isomerism found in the pairs

of structures that are mirror images of each other. These
mirror images = enantiomers, & the 2 members of the pair
are designated as D- & L-sugar.
Ø  Vast majority of sugars in humans are D-sugars .
 Enantiomers
•  Two molecules which are non-superimposable mirror images of
each other (pairs of stereoisomers)
•  They are mirror images that can’t be overlapped.

Figure 7.5
Enantiomers
(mirror images) of
glucose.
 Enantiomers
Ø  Chiral center/stereogenic center
•  Asymmetric carbon - 4 different things are attached to it.

Chiral center
Ø  There must be at least one asymmetric carbon to have
stereoisomers.
 D and L-Enantiomers
C1 at most
oxidized end

Penultimate
carbon

Penultimate (second to last carbon) carbon is the last chiral carbon of the chain.

•  L isomers have the hydroxy (OH) group attached to the left side
of the asymmetric carbon. (Latin: L – levo for left)
•  D isomers have the hydroxy group (OH) on the right side. (Latin:
D- dextro for right)
•  Naturally occurring sugars are D isomers.
 D and L Designations

§  D & L CHO CHO

designations are
based on the H C OH HO C H
configuration
CH2OH CH2OH
about the single
asymmetric C in D-glyceraldehyde L-glyceraldehyde
glyceraldehyde.
CHO CHO
§  The lower
representations H C OH HO C H
are Fischer
Projections. CH2OH CH2OH
D-glyceraldehyde L-glyceraldehyde
 D and L Designations

•  For sugars with

more than one O H O H
chiral center, D or C C
L refers to the H – C – OH HO – C – H
asymmetric C HO – C – H H – C – OH
farthest from the H – C – OH HO – C – H
aldehyde or keto H – C – OH HO – C – H
group.
CH2OH CH2OH
•  M o s t n a t u r a l l y D-glucose L-glucose
occurring sugars
are D isomers.
Ø  The number of stereoisomers is 2n, where n is the number of
asymmetric centers.
Ø  The 6-C aldoses have 4 asymmetric centers. Thus there are 16
stereoisomers (8 D-sugars and 8 L-sugars).
 Aldopentoses: C5, three chiral carbons, eight stereoisomers
CHO CHO CHO CHO
H OH HO H H OH HO H
H OH H OH HO H HO H
H OH H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH

D-ribose D-arabinose D-xylose D-lyxose

25
Aldohexoses: C6, four chiral carbons, sixteen stereoisomers

CHO CHO CHO CHO CHO CHO CHO CHO

H OH HO H H OH HO H H OH HO H H OH HO H
H OH H OH HO H HO H H OH H OH HO H HO H
H OH H OH H OH H OH HO H HO H HO H HO H
H OH H OH H OH H OH H OH H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH

D-allose D-altrose D- glucose D-mannose D-gulose D-idose D-galactose D-talose

 Isomers and epimers
Isomers- compounds that have same chemical formula but
have different structures.
e.g., fructose, glucose, mannose, & galactose are all isomers of
each other, having same formula, C6H12O6.

Note: carbons in sugars are numbered beginning at end

containing the carbonyl C i.e., aldehyde or keto group
 A.  Isomers and epimers

Epimers- If 2 monosaccharides
differ in configuration around only
one specific C atom (with
exception of carbonyl C), they are
defined as epimers of each other
(of course they are also isomers)
e.g.
Ø  glucose & galactose are C-4
epimers, their structures differ
only in the position of
–OH group at C 4.
Ø  Glucose & mannose are C-2
epimers

Figure 7.4
C-2 and C-4 epimers and
an isomer of glucose.
Ø  Galactose & mannose are not epimers, because
they differ in position of –OH groups at two carbons,
and therefore defined only as isomers.

* *
* *
 Cyclic Forms of Monosaccharides

Ø  The dominant form of monosaccharides with 5 or more C

atoms is cyclic.

Ø  Formation of a ring results in creation of an anomeric C at

carbon 1 of an aldose or at carbon 2 of a ketose.

Ø  These structures are designated the α or β configurations

of the sugar, e.g., α-D-glucose & β-D-glucose. They are
both glucose, but are anomers of each other.
Two types of ring structures are possible:

– five-membered ring, or furanose ring, derived from parent

compound furan
– six-membered ring, or pyranose ring, derived from parent
compound pyran
 HAWORTH PROJECTIONS
For D sugars (Aldoses) drawn as Haworth projections, the
designation:

§  α means that the hydroxyl group attached to C-1 is below the
plane of the ring (down)

§  β means that the hydroxyl group attached to C-1 above the plane
of the ring (up)

The C-1 carbon atom is called the ANOMERIC CARBON

ATOM, and the α and β forms are called ANOMERS.
 Cyclic Forms of Monosaccharides
Anomers: Cyclic monosaccharides that differ only in the position
of the substituents on the anomeric carbon atom.
2 anomeric forms of D-glucose:

– Alpha-form: -OH of C1 and CH2OH of C5 are on opposite sides

– Beta-form: -OH of C1 and CH2OH of C5 are on same sides

α-D-glucose β-D-glucose
 Disaccharides
§  The two monosaccharides are linked together by acetal formation
to form disaccharide.
§  One monosaccharide act as a hemiacetal and other as alcohol and
the resulting ether bond is a glycosidic linkage.
Ø  Condensation of the hydroxyl function of the hemiacetal group of one
monosaccharide with the hydroxyl group of another monosaccharide forms the
bond, called a glycosidic bond, joining the 2 saccharide units.
Figure 7.3. A glycosidic bond between two hexoses
producing a disaccharide.
 
Disaccharides
•  A disaccharide is formed when two monosaccharides
undergo condensation reaction which involves the
elimination reaction of a small molecule, such as water,
from the functional groups only.

•  a hydroxyl group on one monosaccharide reacts with the

anomeric carbon of another monosaccharide to form a
glycosidic bond.

•  Each disaccharide has a specific glycosidic linkage

(depending on which hydroxyl reacts with which anomer)

•  Like monosaccharides, disaccharides form aqueous

solutions when dissolved in water.
•  The three most common disaccharides are maltose,
lactose and sucrose.
 Disaccharides
Maltose (reducing sugar)
§  Malt sugar, found in corn syrup, malt, and germinating seeds
§  consists of two molecules of glucose joined by α-1,4-glycosidic
bond.
§  α-1,4-glycosidic bond means that the first sugar is in α-
configuration and its C#1 is linked to C#4 of the second sugar
component.
§  the second sugar may be either an α- or a β-anomer.
Formation of Maltose:
 Lactose (reducing disaccharide)

§  Milk sugar

– human - 7%–8% lactose
– cow’s milk - 4%–5% lactose
§  consists of β-galactose with a
β-1,4-glycosidic linkage to β-
glucose (or α-glucose).
Lactose intolerance: a condition in which people lack the enzyme
lactase needed to hydrolyze lactose to galactose and glucose.
§  Lactose intolerance is unpleasant, but its effects can be avoided
by a diet that rigorously excluded milk and milk products.

Hydrolysis of Lactose:
Lactose intolerance vs Galactosemia

Ø  When undigested, lactose attracts water causing fullness,

discomfort, cramping, nausea, and diarrhea.
Ø  Bacterial fermentation of lactose along the intestinal tract
produces acid (lactic acid) and gas, adding to the discomfort.

Galactosemia: the genetic disease caused by the absence of

the enzymes needed for conversion of galactose to glucose.

Ø  A reduced form of galactose, called dulcitol (galactitol), a

toxic metabolite, is produced and accumulates.
Ø  If galactosemia is not treated, it leads to severe mental
retardation, cataracts, and early deaths
 Sucrose (nonreducing disaccharide)
Ø  the common table sugar & the most abundant of all
disaccharides found in plants.
Ø  produced commercially from the juice of sugar cane and sugar
beets.
Ø  the α-anomeric carbon 1 of glucose joins the β-anomeric
carbon 2 of fructose (α-1,2-glycosidic bond)
 Hydrolysis of Sucrose
•  Sucrose is hydrolyzed by the enzyme sucrase (or
invertase), which is secreted in the small intestine.
•  The glucose and fructose can then be absorbed into the
bloodstream (disaccharides are too large to be absorbed)
Cellobiose (reducing disaccharide)

Ø  one of the major fragments isolated after extensive hydrolysis

of cellulose.
Ø  the 2 glucose units are joined by a β-1,4-glycosidic linkage

Ø  Maltose is digested easily by humans because we have

enzymes that can break α-(1◊4) linkages but not β-(1◊4)
linkages of cellobiose.
 Hydrolysis of Disaccharides:
Ø  When hydrolyzed using acid or an enzyme, the following
monosaccharides are produced:
H +, Δ
C12H22O11 + H2O C6H12O6 + C6H12O6
or
enzyme
Acid
Maltose + H2O or D-Glucose + D-Glucose
enzyme

Acid
Lactose + H2O or D-Glucose + D-Galactose
enzyme

Acid
Sucrose + H2O or D-Glucose + D-Fructose
enzyme
 OLIGOSACCHARIDE SUGARS
Ø  Commonly found in onions, cabbage, broccoli and wheat
• In humans, intestinal bacteria action on the undigestable raffinose
and stachyose present in beans produces gaseous products that
can cause discomfort and flatulence.
Solanin - a potato toxin, is a oligosaccharide found in association with
an alkaloid
•bitter taste of potatoes is due to relatively higher levels of solanin.
Antigens used in the ABO blood group classification
 ABO blood group antigens present on red blood cells

Ø  Type O blood is a universal donor because this blood type lacks antigens on the outside of the red blood cells. This
means that our immune system will not react to the blood because there is no antigen to react against. 
 Blood Transfusion

Ø  For a blood donor and recipient to be ABO compatible for a

transfusion, the recipient must not have Anti-A or Anti-B
antibodies that correspond to the A or B antigens on the
surface of the donor's red blood cells (since the red blood
cells are isolated from whole blood before transfusion, it is
unimportant whether the donor blood has antibodies in its
plasma).

Ø  If the antibodies of the recipient's blood and the antigens on

the donor's red blood cells do correspond, the donor blood is
rejected.
Ø  On rejection, the recipient may experience Acute hemolytic
transfusion reaction.
Blood Group Inheritance
 Polysaccharides
•  A polysaccharide is a polymer consisting of hundreds
to thousands of monosaccharides joined together by
glycosidic linkages.
•  They range in structure from linear to highly branched.

•  Three biologically important polysaccharides include the

storage polysaccharides such as starch, glycogen and
the structural polysaccharides such as cellulose are
polymers of D-glucose, but they differ in the type of
glycosidic bond and/or the amount of branching.

•  Chitin is also a structural polysaccharide.

 Plant Starch (Amylose and Amylopectin)
•  Starches are storage forms of glucose found in plants.

•  Starch contains a mixture of amylose and amylopectin.

•  Amylose is an unbranched polymer (forms α-helix) of D-

glucose molecules linked by α-1,4-glycosidic bonds
•  Amylose usually assumes a helical configuration with six glucose
units per turn.

•  Amylopectin is like amylose, but has extensive branching, with

the branches using α-1,6-glycosidic bonds
Plant Starch (Amylose and Amylopectin)
 Iodine Test for Starch

•  The presence of starch can easily be identified using

iodine (I2)
•  Rows of iodine atoms form in the core of the α-helix
of amylose, forming a dark blue complex
•  Because amylopectin, glycogen and cellulose do not
form α-helices, they do not complex well with
iodine, so do not show the blue color (they show a
purple or brown color)
•  Monosaccharides do not interact with the iodine, so
no color is produced
Hydrolysis of starch
H+, Δ H+, Δ
(C6H10O5)n or
(C6H10O5)x or (C6H10O5)y

starch
enzyme amylodextrin enzyme erythrodextrin
Dark blue complex Purple Reddish brown
(Rx’n with I2 in KI)
- A polyiodide complex H+, Δ or
enzyme

H+, Δ H+, Δ (C6H10O5)z

n C6H12O6 n/2 C12H22O11
or achroodextrin
glucose maltose enzyme
Yellow Yellow brown

Decreasing Molar mass: x >y> z

 Glycogen
•  Glycogen (animal starch) is like amylopectin, except it’s
even more highly branched (occur at intervals of 8-10 glucose
units, while in amylopectin the branches are separated by
12-20 glucose units).
•  animals store glycogen in the liver and muscles (about a one-
day supply in humans) and use it to maintain fairly constant
blood sugar levels between meals.
The Comparison of Starch and Glycogen
Molecules

Figure 4.4
 Cellulose
Cellulose is the major structural polymer in plants.
§  it is an unbranched polymer of D-glucose molecules
linked by β-1,4-glycosidic bonds.
§  cellulose forms β-sheets of parallel strands held together by
hydrogen bonding.
§  we don’t have the enzyme to break down cellulose
§  some animals have microorganisms that do have the
enzyme.
Ø  The role of cellulose is to impart strength and rigidity to
plant cell walls, which can withstand high hydrostatic
pressure gradients.

Ø  This promotes intrachain and interchain hydrogen bonds, as

well as van der Waals interactions, that cause cellulose
chains to be straight and rigid, and pack with a crystalline
arrangement in thick bundles called microfibrils.

Ø  These microfibrils are very strong.

 Chitin
Ø  Chitin is a linear homopolysaccharide of N-acetyl-b-D-
glucosamine, main component of the cell walls of fungi, and
provides structural support for the exoskeleton (shell) of
invertibrates. (eg. Insects, lobsters, shrimp)
Ø  The polymer is linked as β-1,4-units.

N-acetyl-β-D-glucosamine
§  long-chain polymer of a N-acetyl-β-D-glucosamine:
 Glycolipids
Ø  Glycolipids are membrane lipids in which the hydrophilic
head groups are oligosaccharides, which act as specific
sites for recognition by carbohydrate-binding proteins.

Glycoproteins

Ø  Glycoproteins-are molecules that comprise protein and

carbohydrate chains that are involved in many physiological
functions including immunity.
Ø  are protein which contain oligosaccharide chains covalently
attached to amino acid side chains.