Chapter 7 Notes

CHEM 2353
Fundamentals of Organic Chemistry

Chapter
Chapter

7 Carbohydrates

Organic and Biochemistry for Today (4th ed.)

Spencer L. Seager / Michael R. Slabaugh
Mr. Kevin A. Boudreaux
Angelo State University
www.angelo.edu/faculty/kboudrea
1

Carbohydrates and Biochemistry

• Carbohydrates are compounds of tremendous
biological importance:
– they provide energy through oxidation
– they supply carbon for the synthesis of cell
components
– they serve as a form of stored chemical energy
– they form part of the structures of some cells and
tissues
• Carbohydrates, along with lipids, proteins, nucleic
acids, and other compounds are known as
biomolecules because they are closely associated
with living organisms. Biochemistry is the study of
the chemistry of biomolecules and living organisms.
2
Chapter 7 Notes

Classification of
Carbohydrates

Carbohydrates
• Carbohydrates are polyhydroxy aldehydes or
ketones, or substances that yield such compounds on
hydrolysis
H O
C

H C OH

H C OH

H C OH

CH2OH
ribose The term “carbohydrate”
comes from the fact that
when you heat sugars, you
4
get carbon and water.
Chapter 7 Notes

Classes of Carbohydrates
• Monosaccharides contain a single polyhydroxy
aldehyde or ketone unit (saccharo is Greek for
“sugar”) (e.g., glucose, fructose).

• Disaccharides consist of two monosaccharide units

linked together by a covalent bond (e.g., sucrose).

• Oligosaccharides contain from 3 to 10

monosaccharide units (e.g., raffinose).

Classes of Carbohydrates
• Polysaccharides contain very long chains of
hundreds or thousands of monosaccharide units,
which may be either in straight or branched chains
(e.g., cellulose, glycogen, starch).

6
Chapter 7 Notes

The Stereochemistry
of Carbohydrates

Stereoisomers
• Glyceraldehyde, the simplest carbohydrate, exists in
two isomeric forms that are mirror images of each
other:
CHO CHO

HO C H H C OH

CH2OH CH2OH
L-glyceraldehyde D-glyceraldehyde

• These forms are stereoisomers of each other.

• Glyceraldehyde is a chiral molecule — it cannot be
superimposed on its mirror image. The two mirror-
image forms of glyceraldehyde are enantiomers of
each other.
8
Chapter 7 Notes

Chiral Carbons
• Chiral molecules have the same relationship to each
other that your left and right hands have when
reflected in a mirror.
• Achiral objects can be superimposed on the mirror
images — for example, drinking glasses, spheres,
and cubes.
• Any carbon atom which is connected to four
different groups will be chiral, and will have two
nonsuperimposable mirror images; it is a chiral
carbon or a center of chirality.
– if any of the two groups on the carbon are the
same, the carbon atom cannot be chiral.
• Many organic compounds, including carbohydrates,
contain more than one chiral carbon.
9

Examples: Chiral Carbon Atoms

• Identify the chiral carbon atoms (if any) in each of
the following molecules:
H Cl Cl Br

H C H H C H H C Cl H C Cl

H Cl Cl F
OH OH OH

CH3 C CH3 CH3 C CH2Cl CH3 C CH2CH3

H H H

O HO HO
O
CH3 C CH2CH3
10
Chapter 7 Notes

Examples: Chiral Carbons in Carbohydrates

• Identify the chiral carbons (if any) in the following
carbohydrates:
O H
C
CHO CH2OH
H C OH CH2OH
CH OH C O
HO C H O
H C OH OH
CH OH
H C OH
CH2OH H C OH OH OH
H C OH
erythrose CH2OH OH
CH2OH
glucose
11

2n Rule
• When a molecule has more than one chiral carbon,
each carbon can possibly be arranged in either the
right-hand or left-hand form, thus if there are n
chiral carbons, there are 2n possible stereoisomers.

Maximum number of possible stereoisomers = 2n

CH3

CH3

Cholesterol has 28 = 256

possible stereoisomers. (But
HO Nature makes only one!) 12
Chapter 7 Notes

Fischer Projections
• Fischer projections are a convenient way to
represent mirror images in two dimensions.
• Place the carbonyl group at or near the top and the
last achiral CH2OH at the bottom.
CHO CHO

HO C H H C OH

CH2OH CH2OH

CHO CHO

HO H H OH

CH2OH CH2OH
13
L-glyceraldehyde D-glyceraldehyde

Naming Stereoisomers
• When there is more than one chiral center in a
carbohydrate, look at the chiral carbon farthest from
the carbonyl group: if the hydroxy group points to
right when the carbonyl is “up” it is the D-isomer,
and when the hydroxy group points to the left, it is
the L-isomer.

CHO CHO

HO H H OH

HO H H OH

CH2OH CH2OH
L-erythrose D-erythrose

14
Chapter 7 Notes

Examples: Fischer Projections

• Draw Fischer projections
of D and L lactic acid: • Given the structure
for D-glucose, draw
CO2H the structure of L-
CH3 CH OH
glucose:
CHO

H OH

• Draw Fischer projections HO H

of D and L alanine:
H OH
NH2
CH3 CH CO2H H OH

CH2OH
D-glucose 15

Examples: Fischer Projections

• Identify the following compounds as D or L
isomers, and draw their mirror images.

CH2OH
CHO
C O
HO H
HO H
HO H
H OH
H OH
H OH
CH2OH
lyxose CH2OH
fructose

16
Chapter 7 Notes

What’s So Great About Chiral Molecules?

• Molecules which are enantiomers of each other have
exactly the same physical properties (melting point,
boiling point, index of refraction, etc.) but not their
interaction with polarized light.
• Polarized light vibrates only in one plane; it results
from passing light through a polarizing filter.

17

Optical Activity
• A levorotatory (–) substance rotates polarized light
to the left. [E.g., l-glucose; (-)-glucose]
• A dextrorotatory (+) substance rotates polarized
light to the right. [E.g., d-glucose; (+)-glucose]
• Molecules which rotate the plane of of polarized
light are optically active.
• Most biologically important molecules are chiral,
and hence are optically active. Often, living systems
contain only one of all of the possible
stereochemical forms of a compound. In some
cases, one form of a molecule is beneficial, and the
enantiomer is a poison (e.g., thalidomide).

18
Chapter 7 Notes

Monosaccharides

19

Classification of Monosaccharides
• The monosaccharides are the simplest of the
carbohydrates, since they contain only one
polyhydroxy aldehyde or ketone unit.
• Monosaccharides are classified according to the
number of carbon atoms they contain:
No. of Class of
carbons Monosaccharide
3 triose
4 tetrose
5 pentose
6 hexose

• The presence of an aldehyde is indicated by the

prefix aldo- and a ketone by the prefix keto-.
20
Chapter 7 Notes

Classification of Monosaccharides
• Thus, glucose is an aldohexose (aldehyde + 6 Cs)
and ribulose is a ketopentose (ketone + 5 Cs)
O H
C CH2OH
H C OH C O
HO C H H C OH
H C OH H C OH
H C OH CH2OH
CH2OH ribulose
a ketopentose
glucose
an aldohexose
21

Examples: Classifying Monosaccharides

• Classify the following monosaccharides:

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

22
Chapter 7 Notes

The Family of D-aldoses

(L-forms not shown)
CHO
H OH Aldotriose
CH2OH 21 = 2
D-glyceraldehyde

CHO CHO
H OH HO H
Aldotetroses
H OH H OH 22 = 4
CH2OH CH2OH
D-erythrose D-threose

CHO CHO CHO CHO

H OH HO H H OH HO H
H OH H OH HO H HO H Aldopentoses
H OH H OH H OH H OH 23 = 8
CH2OH CH2OH CH2OH CH2OH
D-ribose D-arabinose D-xylose D-lyxose 23

The Family of D-aldoses

(L-forms not shown)

CHO CHO CHO CHO CHO

H OH HO H H OH HO H H OH

H OH H OH HO H HO H H OH
Aldohexoses
H OH H OH H OH H OH HO H 24 = 16
H OH H OH H OH H OH H OH

CH2OH CH2OH CH2OH CH2OH CH2OH

D-allose D-altrose D-glucose D-mannose D-gulose

CHO CHO CHO

HO H H OH HO H
H OH HO H HO H
HO H HO H HO H
H OH H OH H OH
CH2OH CH2OH CH2OH
D-idose D-galactose D-talose
24
Chapter 7 Notes

The Family of D-ketoses

(L-forms not shown)
CH2OH
O Ketotriose
CH2OH 20 = 1
Dihydroxyacetone

CH2OH
O
Ketotetroses
H OH 21 = 2
CH2OH
D-erythrulose

CH2OH CH2OH

O O

H OH HO H Ketopentoses
H OH H OH 22 = 4
CH2OH CH2OH
D-ribulose D-xylulose 25

The Family of D-ketoses

(L-forms not shown)

CH2OH CH2OH CH2OH CH2OH

O O O O

H OH HO H H OH HO H
Ketohexoses
HO H
H OH H OH HO H 23 = 8
H OH H OH H OH H OH

CH2OH CH2OH CH2OH CH2OH

D-Psicose D-Fructose D-Sorbose D-Tagatose

26
Chapter 7 Notes

Physical Properties of Monosaccharides

• Most monosaccharides have a sweet taste (fructose
is sweetest; 73% sweeter than sucrose).
• They are solids at room temperature.
• They are extremely soluble in water:
– Despite their high molecular weights, the
presence of large numbers of OH groups make
the monosaccharides much more water soluble
than most molecules of similar MW.
– Glucose can dissolve in minute amounts of water
to make a syrup (1 g / 1 ml H2O).

27

Physical Properties of Monosaccharides

Table 7.2 The relative sweetness of sugars
(sucrose = 1.00)

Sugar Relative Type

Sweetness
Lactose 0.16 Disaccharide
Galactose 0.22 Monosaccharide
Maltose 0.32 Disaccharide
Xylose 0.40 Monosaccharide
Glucose 0.74 Monosaccharide
Sucrose 1.00 Disaccharide
Invert sugar 1.30 Mixture of glucose and fructose
Fructose 1.73 Monosaccharide
28
Chapter 7 Notes

Chemical Properties of Monosaccharides

• Monosaccharides do not CH2OH
usually exist in solution in H
their “open-chain” forms: H
C O

an alcohol group can add H O

C
into the carbonyl group in OH H C
the same molecule to form HO
C C H
a pyranose ring containing
a stable cyclic hemiacetal H OH

or hemiketal. D-glucose
CH2OH CH2OH

H C O C O
OH H H
O C
H
C C
H
C
OH H OH H
HO H HO OH
C C C C

a pyranose ring H OH cyclic H OH

β-D-glucose hemiacetals α-D-glucose
29
β-up α-down

Glucose Anomers
O H
CH2OH C CH2OH
1
H C OH OH
O O
OH HO C H OH
1 1
H C OH
OH OH OH
H C OH
Haworth OH OH
structures CH2OH
α-D-glucose D-glucose β-D-glucose
36% 0.02% 64%

• In the pyranose form of glucose, carbon-1 is chiral,

and thus two stereoisomers are possible: one in
which the OH group points down (α-hydroxy group)
and one in which the OH group points up (β-
hydroxy group). These forms are anomers of each
other, and carbon-1 is called the anomeric carbon. 30
Chapter 7 Notes

Fructose Anomers
• Fructose closes on itself to form a furanose ring:
H
CH2OH O
O O
OH
CH2OH
a furanose ring

OH
D-fructose
β-hydroxy
CH2OH CH2OH CH2OH OH
O O
HO HO

OH α-hydroxy CH2OH
OH OH
α-D-fructose β-D-fructose 31

Drawing Furanose and Pyranose Rings

• Monosaccharides are often represented using the
Haworth structures shown below for furanose and
pyranose rings.
• The remaining OH groups on the ring point up or
down depending on the identity of the sugar.

always above ring

for D-saccharides
CH2OH
CH2OH
O O

Furanose Pyranose
ring ring
32
Chapter 7 Notes

Examples: Anomers
With Friends Like These, Who Needs Anomers?

• Identify the structures below as being the α- or β-

forms, and draw the structure of their anomers:

CH2OH OH CH2OH
O OH O
OH

OH
OH OH
ribose OH
galactose

33

Oxidation of Monosaccharides
• Aldehydes and ketones that have an OH group on
the carbon next to the carbonyl group react with a
basic solution of Cu2+ (Benedict’s reagent) to form
a red-orange precipitate of copper(I) oxide (Cu2O).
• Sugars that undergo this reaction are called
reducing sugars. (All of the monosaccharides are
reducing sugars.)

oxidation
Reducing sugar + Cu2+ product
+ Cu2O
deep blue red-orange
solution ppt

34
Chapter 7 Notes

Formation of Phosphate Esters

O
O
–
O P O CH2 –
O P O CH2 OH
– O
O O
OH O– HO

CH2OH
OH OH
OH
OH fructose 6-phosphate
glucose 6-phosphate
• Phosphate esters can form at the 6-carbon of
aldohexoses and aldoketoses.
• Phosphate esters of monosaccharides are found in
the sugar-phosphate backbone of DNA and RNA, in
ATP, and as intermediates in the metabolism of
carbohydrates in the body. 35

Glycoside Formation
• The hemiacetal and hemiketal forms
of monosaccharides can react with CH2OH
alcohols to form acetal and ketal
structures called glycosides. The O
new carbon-oxygen bond is called OH
the glycosidic linkage.
OH OCH3
CH2OH
OH
O methyl α-D-glycopyranoside
OH H+ +
+ CH3OH
CH2OH
OH OH OCH3
O
OH OH
α-D-glucose
OH
OH 36
methyl β-D-glycopyranoside
Chapter 7 Notes

Glycoside Formation
• Once the glycoside is formed, the ring can no longer
open up to the open-chain form. Glycosides,
therefore, are not reducing sugars.

Glycoside + Cu2+ NR

37

Examples: Glycoside Formation

• Identify the glycosidic linkage in each of the
following molecules:

CH2OH
CH2OH OCH3
OH
O O
OH
CH2OH
OCH2CH3
OH OH
OH

38
Chapter 7 Notes

Important Monosaccharides
CH2OH OH CH2OH OH
O O

OH OH OH
β-D-ribose CH2OH β-D-deoxyribose
Forms the sugar backbone of Forms the sugar backbone of
ribonucleic acid (RNA) OH O
OH deoxyribonucleic acid (DNA)
OH

OH
β-D-galactose
Incorporated with glucose
into lactose (milk sugar) 39

Important Monosaccharides
CH2OH
OH
O HO
OH
OH
OH
β-D-glucose
Also known as dextrose and blood
sugar; present in honey and fruits.
Glucose is metabolized in the body
for energy. Other sugars absorbed
into the body must be converted to
glucose by the liver.
CH2OH OH
O
CH2OH
OH
β-D-fructose
Also known as levulose and fruit
sugar. Fructose is the sweetest of
the monosaccharides. It is present
in honey (1:1 ratio with glucose),
fruits, and corn syrup. It is often
used to sweeten foods, since less
fructose is needed to achieve the
same degree of sweetness.

40
Chapter 7 Notes

Disaccharides

41

Disaccharides
• Two monosaccharides can be linked together
through a glycosidic linkage to form a disaccharide.

CH2OH CH2OH

O O
OH OH
+

OH OH OH OH
OH OH cyclic hemiacetal
α-D-glucose α-D-glucose

CH2OH CH2OH

O O
OH OH
+ H2O
O
OH OH
OH OH 42
α(1→4) glycosidic linkage Maltose
Chapter 7 Notes

Important Disaccharides
CH2OH
β(1→4) glycosidic linkage
O
CH2OH OH
OH
O O
CH2OH CH2OH OH OH
OH
O O α-D-glucose
OH OH β-D-galactose
O OH Lactose
OH OH Also known as milk sugar.
α-D-glucose OH α-D-glucose
OH Lactose constitutes 5% of cow's
Maltose milk and 7% of human milk. It is
Also known as malt sugar. It digested by the enzyme lactase.
is found in germinating grain
(such as barley), and is formed
during the hydrolysis of starch
to glucose during digestion.
Because it has a hemiacetal
group, it is a reducing sugar. 43

Important Disaccharides
CH2OH Sucrose
Also known as table sugar. Both anomeric
O α-D-glucose carbons of glucose and fructose are tied
OH together in the glycosidic linkage; thus neither
ring can open, and sucrose is not a reducing
α−1 → β−2 sugar. Sucrose is abundant in sugar cane
OH and sugar beets; maple syrup contains about
O glycosidic
CH2OH OH linkage 65% sucrose, with glucose and fructose
O present as well; caramel is the solid residue
β-D-fructose formed from heating sucrose. A flavoring
HO agent called invert sugar is produced by the
CH2OH hydrolysis of sucrose under acidic conditions,
which breaks it apart into glucose and
OH fructose; invert sugar is sweeter than sucrose
OH
because of the fructose. Some of the sugar
found in honey is formed in this fashion;
O
HO OH invert sugar is also produced in jams and
HO O OH jellies prepared from acid-containing fruits.
OH
O
OH
OH
44
Chapter 7 Notes

Oligosaccharides

45

Oligosaccharides
• Oligosaccharides contain from 3 to 10
monosaccharide units.

CH2OH
HOCH2
O O
CH2OH OH HO
OH O
O O
OH CH2OH
OH
OH β-D-fructose
α-D-glucose
β-D-galactose
OH Raffinose
An oligosaccharide found in peas and beans;
largely undigested until reaching the intestinal
flora in the large intestine, releasing hydrogen,
carbon dioxide, and methane)

46
Chapter 7 Notes

Polysaccharides

47

Polysaccharides
• Polysaccharides contain hundreds or thousands of
carbohydrate units.
• Polysaccharides are not reducing sugars, since the
anomeric carbons are connected through glycosidic
linkages.
• We will consider three kinds of polysaccharides, all
of which are polymers of glucose: starch, glycogen,
and cellulose.

48
Chapter 7 Notes

Starch
• Starch is a polymer consisting of D-glucose units.
• Starches (and other glucose polymers) are usually
insoluble in water because of the high molecular
weight, but they can form thick colloidal
suspensions with water.
• There are two forms of starch: amylose and
amylopectin.

49

Starch — Amylose
• Amylose consists of long, unbranched chains of
glucose (from 1000 to 2000 molecules) connected
by α(1→4) glycosidic linkages.
• 10%-20% of the starch in plants is in this form.
• Amylose forms helices (coils) which can trap
molecules of iodine, forming a characteristic deep
blue-purple color. (Iodine is often used as a test for
the presence of starch.)

CH2OH CH2OH CH2OH

O O O
OH OH OH
O O O O

OH OH OH
α(1→4) glycosidic linkage
50
Chapter 7 Notes

Starch — Amylopectin
• Amylopectin consists of long chains of glucose (up
to 105 molecules) connected by α(1→4) glycosidic
linkages, with α(1→6) branches every 24 to 30
glucose units along the chain.
• 80%-90% of the starch in plants is in this form.
CH2OH
O
OH
O α(1→6) branch point
O
OH
CH2OH CH2 CH2OH
O O O
OH OH OH
O O O O

OH OH OH 51
α(1→4) glycosidic linkage

Glycogen
• Glycogen, also known as animal starch, is
structurally similar to amylopectin, containing both
α(1→4) glycosidic linkages and α(1→6) branch
points.
• Glycogen is even more highly branched, however,
with branches occuring every 8 to 12 glucose units.
• Glycogen is abundant in the liver and muscles; on
hydrolysis it forms glucose, which maintains normal
blood sugar level and provides energy.

Amylose

Amylopectin/Glycogen

52
Chapter 7 Notes

Cellulose
• Cellulose is a polymer consisting of long,
unbranched chains of D-glucose connected by
β(1→4) glycosidic linkages; it may contain from
300 to 3000 glucose units in one molecule.

CH2OH
O
CH2OH OH
O O
O
CH2OH OH
OH
O O
β(1→4) glycosidic linkage
OH
OH
O

OH
53

Cellulose
• Because of the β-linkages, cellulose has a different
overall shape from amylose, forming extended
straight chains which hydrogen bond to each other,
resulting in a very rigid structure.
• Cellulose is an important structural polysaccharide,
and is the single most abundant organic compound
on earth. It is the material in plant cell walls that
provides strength and rigidity; wood is 50%
cellulose.
• Most animals lack the enzymes needed to digest
cellulose, although it does provide needed roughage
(dietary fiber) to stimulate contraction of the
intestines and thus help pass food along through the
digestive system.

54
Chapter 7 Notes

Cellulose
• Some animals, such as cows, sheep, and horses, can
process cellulose through the use of colonies of
bacteria in the digestive system which are capable of
breaking cellulose down to glucose; ruminants use a
series of stomachs to allow cellulose a longer time to
digest. Some other animals such as rabbits reprocess
digested food to allow more time for the breakdown
of cellulose to occur.
• Cellulose is also important industrially, from its
presence in wood, paper, cotton, cellophane, rayon,
linen, nitrocellulose (guncotton), photographic films
(cellulose acetate), etc.

55

Nitrocellulose, Celluloid, and Rayon

• Guncotton (German, schiessbaumwolle) is cotton which has been treated
with a mixture of nitric and sulfuric acids. It was discovered by Christian
Friedrich Schönbein in 1845, when he used his wife’s cotton apron to
wipe up a mixture of nitric and sulfuric acids in his kitchen, which
vanished in a flash of flame when it dried out over a fire. Schönbein
attempted to market it as a smokeless powder, but it combusted so readily
it was dangerous to handle. Eventually its use was replaced by cordite
(James Dewar and Frederick Abel, 1891), a mixture of nitrocellulose,
nitroglycerine, and petroleum jelly, which could to extruded into cords.
• Celluloid (John Hyatt, 1869) was the first synthetic plastic, made by
combining partially nitrated cellulose with alcohol and ether and adding
camphor to make it softer and more malleable. It was used in
manufacturing synthetic billiard balls (as a replacement for ivory),
photographic film, etc.; it was eventually replaced by less flammable
plastics.
• Rayon (Louis Marie Chardonnet, 1884) consists of partially nitrated
cellulose mixed with solvents and extruded through small holes, allowing
the solvent to evaporate; rayon was a sensation when introduced since it
was a good substitute for silk, but it was still highly flammable.

56
Chapter 7 Notes

How Sweet It Is!

Sugar Substitutes

57

Saccharin
O

NH
S

O O
Saccharin
The first of the artificial sweeteners, saccharin is noncaloric and
about 500 times sweeter than sugar. It was discovered in 1879
by Constantine Fahlberg, a chemistry student at Johns Hopkins
University working for Ira Remsen; he noticed that the bread he
was eating was unusually sweet, and went back to his lab bench
and tasted all of the compounds he had been working with that
day to find the compound responsible. It was marketed
commercially as a non-nutritive sweetener very quickly,
especially for use by diabetics. It was banned in some areas for
some time because it was a suspected carcinogen.
58
Chapter 7 Notes

Aspartame (NutraSweet)
O OCH3
O

O
N
Aspartame (NutraSweet)
H NH2 OH
Aspartame (NutraSweet) is about 160 times sweeter than sugar; it
is composed of the amino acids aspartic acid and phenylalanine,
neither of which has a sweet taste. It was discovered at Searle by
James Schlatter in 1965, who was preparing intermediates for the
synthesis of a tetrapedtide for an anti-ulcer project. Schlatter had
spilled some of the dipeptide intermediate on his hands, and
noticed later that there was a strong, sweet taste; he went back to
his bench and tasted the dipeptide and found that it indeed was
extremely sweet. Aspartame is sensitive to heat, so it cannot be
used in cooked foods, and it decomposes slowly in liquids,
reducing their shelf life. 59

H O

N
OSO2- N– K+

Cyclamate
Discovered by Michael Sveda in
1937, who noticed that a cigar that
he was smoking in the lab tasted
especially sweet. Cyclamates were
banned by the FDA in 1970.
S O
CH3 O
O
Acesulfame-K (Sunette)
Approved by the FDA in 1988;
200 times sweeter than sugar;
noncaloric; heat-stable and can
be used during cooking

60
Chapter 7 Notes

CH2OH

H OH CH2OH
Cl ClCH2
O O
HO H OH HO
O
H OH CH2Cl
"galactose" OH
OH "fructose"
H OH
Sucralose
CH2OH A non-caloric artificial sweetener
Sorbitol approved by the FDA in 1998.
A sugar alcohol; incompletely The glucose in sucrose is replaced
absorbed during digestion, and by a galactose, and three of the OH
contribute fewer calories than groups are replaced by Cl atoms.
carbohydrates; found naturally in The molecule still tastes sweet, but
fruits; used commercially in is not metabolized in the body.
sugar-free candies, cookies,
chewing gum, etc.
61

The Maillard Reaction

• The Maillard Reaction occurs between foods
containing carbohydrates and proteins under heating;
it results in a complex mixture of products and the
development of a brown color. It is observed in the
grilling or browning of meats, the formation of crust
on baked breads, the boiling of maple syrup, the
brewing of beer, the roasting of coffee and cocoa
beans, the roasting of nuts, and other sources. In
addition to the darkened colors, many complex
flavors are developed. There are hundreds of
compounds produced during these reactions, not
many of which are well-characterized.

H
O
Furfural O

62
Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Chapter 12 Lecture Notes: Carbohydrates

Educational Goals

1. Given a Fischer projection of a monosaccharide, classify it as either aldoses or ketoses.

2. Given a Fischer projection of a monosaccharide, classify it by the number of carbons it contains.
3. Given a Fischer projection of a monosaccharide, identify it as a D-sugar or L-sugar.
4. Given a Fischer projection of a monosaccharide, identify chiral carbons and determine the number
of stereoisomers that are possible.
5. Identify four common types of monosaccharide derivatives.
6. Predict the products when a monosaccharide reacts with a reducing agent or with Benedict’s reagent.
7. Define the term anomer and explain the difference between α and β anomers.
8. Understand and describe mutarotation.
9. Given its Haworth projection, identify a monosaccharide either a pyranose or a furanose.
10. Identify the anomeric carbon in Haworth structures.
11. Compare and contrast monosaccharides, disaccharides, oligosaccharides, and polysaccharides.
12. Given the structure of an oligosaccharide or polysaccharide, identify the glycosidic bond(s) and
characterize the glycosidic linkage by the bonding pattern [for example: β(1⟶4)].

13. Given the Haworth structures of two monosaccharides, be able to draw the disaccharide that is
formed when they are connected by a glycosidic bond.
14. Understand the difference between homopolysaccharides and heteropolysaccharides.
15. Compare and contrast the two components of starch.
16. Compare and contrast amylopectin and glycogen.
17. Identify acetal and hemiacetal bonding patterns in carbohydrates.

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Introduction to Carbohydrates
Carbohydrates are also known as_______________________.
Carbohydrates are an abundant biomolecule.
• More than 50% of the carbon in organic compounds is found in carbohydrates
• Plants use photosynthesis to store energy in__________________, a simple sugar

6 CO2 + 6 H2O + Energy à C6H12O6 + 6 O2

Carbohydrates are a large class of naturally occurring polyhydroxy ___________________and

________________________.

• ________________________(also known as simple sugars) are the simplest carbohydrates containing

3-7 carbon atoms. A sugar containing:

– an aldehyde is known as an ______________________

– a ketone is known as a _________________________

Classification of Carbohydrates
Carbohydrates are grouped into 3 classes:

• ___________________________ are the simplest sugars and serve as the building blocks of larger
molecules
– Example: Glucose

• __________________________ contain 2-10 monosaccharides bonded together (building

block = residue)
– Example: Sucrose

• _____________________________contain more than 10 residues

– Example: Complex Carbohydrates
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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Monosaccharides

Monosaccharides are _____________________________ ketones or aldehydes with 3 or more carbons.

Naming Monosaccharides

Carbohydrate nomenclature is unique to

“sugar chemistry” — we do not name
monosaccharides using the IUPAC rules.

• Monosaccharide names end in

“ose."

• Monosaccharides can be classified

by:

• Carbonyl group:

______________________

or _______________________

• ______________________ of
carbons: triose, tetrose, etc.

• Both: aldotriose, ketotriose, and so

on…

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Examples:

You try it:

Name each of the following monosaccharides as an aldose or ketose & according to its number of C atoms.

_________________________ ______________________________ _____________________

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Stereoisomers in Carbohydrates
Carbohydrates are ________________________molecules since they have carbon atoms carrying four
different groups.

The simplest three-carbon sugar is glyceraldehyde. This sugar exists as a pair of ___________________.

• Enantiomers have the same _______________ physical properties except they behave differently in
the way they rotate polarized light and the way they are affected by catalysts.

Remember: Compounds with n chiral carbon atoms has a maximum of 2n possible stereoisomers and half that
many pairs of enantiomers (mirror images).

• The aldotetrose (below), has 2 chiral carbon atoms and a total of 22 = 4 possible stereoisomers (2 pairs
of enantiomers).

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

The D and L Families of Sugars: Drawing Sugar Molecules

Fischer Projections represent three-dimensional structures of stereoisomers on a flat page.
• A chiral carbon atom is represented in the Fisher projection as the

___________________of two crossed lines.

• Bonds that point __________________ the page are shown as horizontal lines.

• Bonds that curve _________________ _______ ______________the page are shown as vertical
lines.
• In a Fischer projection, the aldehyde or ketone carbonyl group of a monosaccharide is always placed
toward the top of the page.

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Example:
Glucose

Monosaccharides are divided into _________________ families:

• D form and L form sugars.

• D: the –OH group on the chiral C furthest from the C=O comes out of the plane of paper

and points to the_______________________.

• L: the –OH group on the chiral C furthest from the C=O comes out of the plane of paper

and points to the ______________________.

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Monosaccharides
We will briefly survey some important pentoses and hexoses, and their
derivatives.

D-glucose, also called ___________________or_________________

___________________________, is the most important monosaccharide

in human metabolism.

D-fructose, or fruit sugar, is most common natural ketose

• Honey is 40% fructose

Monosaccharide Derivatives

In ________________ __________ a hydrogen atom replaces one or more of the -OH groups in a
monosaccharide.

• D-ribose and its derivative D-2-deoxyribose

(deoxy = minus one oxygen atom) are found in various
coenzymes and in DNA.

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Monosaccharide Derivatives (continued)

In __________________ _______________an -OH group of a

monosaccharide has been replaced by an amino (-NH2) group.

• D-glucosamine is an example.

• D-glucosamine is an amino derivative in which an amino group

replaces one hydroxyl group

In __________ ________________the carbonyl group of a monosaccharide has been reduced to an

alcohol group.
o Sorbitol is an example.

Sorbitol and Xylitol are used as sweeteners

Ribitol is found in the coenzyme FAD

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Monosaccharide Derivatives
(continued)

• In ______________ ______ sugars, an

aldehyde group of a monosaccharide has
been oxidized to form a carboxyl group

D-Gluconic Acid is an example.

Reactions of Monosaccharides
Reactions of monosaccharides are reactions of carbonyl and hydroxyl groups (chapter 11).
• Aldehyde and ketone groups can be reduced
• Aldehyde and alcohol groups can be oxidized

Reduction of Monosaccharides
• The reduction of the C=O group in
an aldehyde or ketone produces

_____________ _______________.

Oxidation of Monosaccharides

The oxidation of the aldehyde C=O group

produces __________________________

_______________ _________________ .

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Oxidation of Monosaccharides (continued)

Benedict’s reagent is a copper compound that will oxidize only _________________ ________________
(aldoses) and not alcohols.

A sugar that reacts with

Benedict’s solution is called a
reducing sugar since it reduces
the ion Cu2+ à Cu+

NOTE: Some ketoses give positive results for Benedict’s test because they ______________________ to
aldehydes in the strongly basic Benedict solution.

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Monosaccharides: Their Cyclic Form

Review:
A hydroxyl group in a monosaccharide can react with the carbonyl to form a _________ _____________

• Hemiacetals are made by the reaction of an _________________with an ___________________.

A hemiacetal contains a C atom bonded to an ______________ and an ________________group.

A monosaccharide contains both an alcohol and an aldehyde group.

• It can react with _____________ to form a cyclic hemiacetal.

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Open Chain to Cyclic Form Mechanism (MECHANISM NOT ON EXAM)

Cyclic forms of monosaccharides are usually drawn with the Haworth Projection in which the ring is viewed
from the side at an angle.
• The edge of the ring closest to the viewer is drawn with a bold line for perspective.
• Substituents on the ring in a Haworth projection are either “up” or “down”

The pair of cyclic hemiacetals with the OH on the hemiacetal carbon in different positions are called

__________________.
• For D-sugars, the α-anomer has the OH pointing ________________
• For D-sugars, the β-anomer has the OH pointing ________________

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

• Example: The open-chain form of D-galactose with its cyclic anomers.

In solution, the open chain and cyclic forms of a monosaccharide are in______________________:

• If we start with a pure open chain or cyclic form in solution, the optical rotation of the solution will
change until equilibrium is achieved and the concentrations of the different forms remain constant.

• The change in optical rotation observed as the system approaches equilibrium is called

________________________.

The cyclic forms of monosaccharides can be

named as derivatives of the
heterocyclic ethers furan (5 members) and
pyran (6 members).

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Example: The aldopentose D-ribose forms a cyclic _____________ (the deoxy form is also shown below)

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Oligosaccharides
Oligosaccharides are short polymers containing 2-10 monosaccharide _________________________.

The residues are bonded to each other by

___________________ _____________.

A glycosidic bond is the ether linkage formed when an acetal is made by reacting a

__________________ of a monosaccharide with a __________________on another sugar.

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

The glycosidic bond in maltose is referred to as an __________________ bond since the monosaccharide on
the left reacts it’s α-anomer hemiacetal at C-1 with a hydroxyl at C-4 on the second monosaccharide.

Formation of α and β anomers

The glycosidic bond can be either ________ or_________.

– Example: Cellobiose is a disaccharide formed when the polysaccharide cellulose is broken down.
– A disaccharide is composed of two monosaccharide residues.
– Cellobiose is made by connecting two glucose molecule by a β(1à4) glycosidic bond.
– Cellobiose cannot be used as a source of glucose by humans since we lack the enzyme to
hydrolyze the glycosidic bond.

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Example: Lactose is a disaccharide found in milk

• Lactose consists of a galactose connected to a glucose residue by a β(1à4) glycosidic bond
• Sounds like cellobiose! But the OH on C-4 is up in galactose and down in glucose
Lactose intolerance is the inability to hydrolyze lactose due to an enzyme deficiency.

Sucrose, or table sugar, is a disaccharide with two twists: ___________________ _______________

and___________ ____________________________.
• The glycosidic bond in sucrose is formed between the hemiacetal C of α-glucopyranose and the
hemiacetal C of β-fructofuranose
• This is an α,β-(1↔2) glycosidic bond

18
Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Note that, as is the case with monosaccharides, the oligosaccharides can be in equilibrium with their anomers

Only the end, hemiacetal residue can open and close

19
Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Most common oligosaccharides are disaccharides

The following are found in peas and beans

Raffinose (a trisaccharide composed of three monosaccharide residues)
Stachyose (a tetrasaccharide composed of four monosaccharide residues)
Verbascose (a pentasaccharide composed of four monosaccharide residues)

These oligosaccharides are indigestible since they contain galactopyranose residues involved in α-(1à6)
glycosidic bonds that humans lack the enzyme to hydrolyze.

_____________________ are sugar-containing lipids that:

• Are present in nerve cell membranes.
• Serve as identifying markers on cell surfaces.
The hemiacetal of a sugar residue is connected to alcohol group of a lipid by a ________________ bond.

20
Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

“How Sweet It Is!”

• Sweetness is rated in comparison to sucrose, which is assigned a sweetness = 100
• Sweeteners used in our foods can be divided into two classes: natural and artificial
– Natural Sweeteners are sugars or derivatives
– Artificial Sweeteners may bear no similarity to sugars!

Artificial Sweeteners:

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Polysaccharides
___________________________ contain 10 or more residues

o In a_________________________, all the residues are the same monosaccharide

o In a_________________________, the residues are built from more than one type of
monosaccharide

o The primary functions of polysaccharides are to:

• ___________________________ (e.g. cellulose)

• __________________ ________________ (e.g. starch and glycogen)

• Cellulose is a homopolysaccharide consisting of long, linear chains of glucose residues joined by β-(1à4)
bonds

• Cellulose is so strong because the linear chains can form _________________ hydrogen bonds with
adjacent chains forming sheets of the polymer

• Wood is about 50% cellulose

• Bacteria in horses, cows, and

termites have enzyme cellulase to hydrolyze
β-(1à4) bonds

22
Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Starch is a homopolysaccharide used by some plants to store energy; there are 2 components of starch:

• 1) _____________________________

• 2) _____________________________

Starch: Amylose
Amylose contains chains of glucose residue connected by α-(1à4) glycosidic bonds.

• Unlike cellulose, amylose chains are not linear but coil

into a_________________.

Starch: Amylopectin
Amylopectin is the other component of starch.

Amylopectin is similar to amylose in that it contains glucose residues linked by α-(1à4) glycosidic

bonds, BUT in amylopectin this chain ____________________ through additional α-(1à6) glycosidic bonds
to residues in other chains.

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

Starch: Amylopectin (continued)

• This branched polysaccharide can be “pruned” simultaneously at

numerous points allowing the glucose residues (and their energy)
to be released more quickly!

________________________, or animal starch, is very similar to amylopectin, except that the chains in
glycogen branch more frequently.

• In amylopectin (right), branches occur every 25 to 30 residues

• In glycogen (left), branches occur every 8 to 12 residues

________________________is a homopolysaccharide of the glucose derivative N-acetyl-D-glucosamine.

-Chitin makes up the hard exoskeleton of crustaceans and insects.

-The polymer chains hydrogen bond to each other leading to chitin’s rigidity.

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Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

An example of a heteropolysaccharide is hyaluronic acid.

Hyaluronic acid is found in the lubricating fluid that surrounds joints, and also in the vitreous humor inside
the eye.

25
Chemistry 108 Chapter 12 Lecture Notes Carbohydrates

26
Name: ____________________________________________________ Pd: ________

Carbohydrates Worksheet

1. Organic molecules all contain the element _______________________.

2. What element(s) are in carbohydrates? _____________________________________________

3. Plants use this polysaccharide to make their cell walls. _____________________________________

4. True or False Carbohydrates are joined together by peptide bonds.

5. True or False A disaccharide is an example of a carbohydrate.

6. True or False Monosaccharides are made of polysaccharides.

7. True or False Monosaccharides have to be broken down many times during digestion.

8. True or False Polymers are made of monomers.

9. True or False Polysaccharides are the simplest form of carbohydrates

10. _____________________ Carbohydrates provide quick/instant energy while ___________________ carbohydrates provide
long term energy.
11. _____________________ is the most common type of Carbohydrate in our diets. (Found in bread/potatoes)

12. Give an example of a type of monosaccharide _____________________________________

a. What food can this be found in? ___________________________________________________________

13. Give an example of a type of polysaccharide ______________________________________

a. What food can this be found in? ___________________________________________________________

14. What is the chemical formula for all monomers of carbohydrates? _________________________________

15. Label the three monosaccharides in the pictures below.

a. Are these monomers or polymers? __________________________
b. What characteristics determines which monosaccharide it is? __________________________
c. The three monosaccharides below have the same chemical formula, but different shapes, so they are known as
_____________________________.

16. The chemical combination of two simple sugar molecules makes sucrose which is a common: __________________________
17. Starches are to Monosaccharides as Polymers are to ____________________.
 18. Draw a glycogen molecule. Be sure to label the elements/atoms.
a. What is its purpose? __________________________________________________

b. Where is it stored? _________________________________________

19. Draw a starch molecule. Be sure to label the elements/atoms.

a. What type of organisms store lots of starch? ______________________________

Carbohydrate Levels of Organization

Monomer: ___________________________
Example Found in (food)

“In-Between”___________________________

Example Found in (food)

Polymer___________________________

Example Found in (food)