BIOCHEM REVIEWER * When sugar (sucrose) and sulfuric acid are
combined, water is removed from the sugar,
INTRO: CARBOHYDRATES
v molecules of exceptional utility
v provide:
basic diets (starch and sugar);
roofs over our heads;
clothes for our bodies (cellulose).
v thicken our ice cream, stick postage stamps to
our letters, and provide biodegradable plastic
trash sacks.
v one of the premier classes of
biochemicals
CARBOHYDRATES: A FIRST CLASS OF BIOCHEMICALS
v most widespread and important biochemical;
found in plants except water
v one of the three principal classes of energy-
yielding nutrients; the other two are fats
and proteins.
v The name carbohydrates was given by French
scientists, who called them hydrates de
carbone because their empirical for-
mulas approximated (C x H2O)n
*not all substances classified as carbohydrates
conform to this formula (e.g., rhamnose,
C6H12O5, and deoxyribose, C5H10O4).
v generally defined as "polyhydroxy aldehydes or
polyhydroxy ketones or substances that yield
these compounds when hydrolyzed"
v The simplest carbohydrates are glyceraldehyde
and dihydroxyacetone:
v “polyhydroxy”: each molecule has more than one
hydroxyl group
leaving a black column of carbon.
CLASSIFICATION OF CARBOHYDRATES
1. Monosaccharide
- cannot be hydrolyzed to simpler carbohydrate
units
- the basic carbohydrate unit of cellular
metabolism
2. Disaccharide
- yields two monosaccharides—either alike or
different—when hydrolyzed:
- often used by plants or animals to transport
monosaccharides from one cell to another
*The monosaccharides and disaccharides generally
have names ending in -ose—for example, glucose,
sucrose, and lactose. These water-soluble car-
bohydrates, which have a characteristically sweet
taste, are also called sugars.
3. Oligosaccharide
- has two to six monosaccharide units linked
together. Oligo comes from the Greek word
"oligos", which means “small or few.”
*Free oligosaccharides that contain more than two
monosaccharide units are rarely found in nature
4. Polysaccharide
- starch and cellulose
- starch: polymer of a-D-glucopyranose
- cellulose: polymer of b-D-glucopyranose
*As a consequence, starch is easily digested by
humans, but we are totally unable to digest
cellulose.
- a macromolecular substance that can be
hydrolyzed to yield many monosaccharide
units:
- structural supports (in plants)
 - storage depot (for monosaccharides), which
cells use for energy

* Originally, mono- and disaccharides were

grouped together as the simple sugars —
carbohydrates that were easily digested and that
produced a rapid increase in blood sugar after a
meal.

* Oligo- and polysaccharides were placed in the

complex carbohydrate category — carbohydrates
that would release glucose more slowly during
The letters D and L do not in any way refer to the
digestion.
direction of optical rotation of a carbohydrate. The
D and L forms of any specific compound are
* Glycemic index: nutritionists rank
enantiomers (e.g., D- and L-glucose).
carbohydrates via this. An experimental measure
of a carbohydrate’s impact on blood sugar relative
4. As a (+) or (-) isomer, depending on whether
to a standard, either glucose or white bread.
the monosaccharide rotates the plane
Higher glycemic index: greater risk of diabetes
of polarized light to the right (+) or to the left (-).
(Type 2) and coronary heart disease.
That is, if a carbohydrate has a low glycemic
EXAMPLES
index, it is probably a healthier food.

Write projection formulas for (a) L-aldotriose, (b)

CLASSIFICATION OF MONOSSACHARIDE
D-ketotetrose, (c) D-aldopentose
1. As a triose, tetrose, pentose, hexose, or
L-aldotriose
heptose:

(a) Triose indicates a three-carbon

* A monosaccharide can have any number of
carbons greater than three, but only
monosaccharides of three to seven carbons are
commonly found in the biosphere.
carbohydrate; aldo indicates that the compound is
an aldehyde; L- indicates that the OH on carbon 2
(adjacent to the terminal CH2OH) is on the left.
The aldehyde group is carbon 1:

2. As an aldose or ketose, depending on

whether an aldehyde group ( --CHO) or keto group
is present.

* For ketoses, it is normally located on carbon 2.

3. As a D or L isomer, depending on the spatial D-ketotetrose

orientation of the --H and --OH groups.
(b) Tetrose indicates a four-carbon
D isomer. OH is in the right carbohydrate; keto indicates a ketone group (on
L isomer. OH is in the left carbon 2); D- indicates that the OH on carbon 3
(adjacent to the terminal CH2OH) is on the right.
Carbons 1 and 4 have the configuration of primary
alcohols:
D-aldopentose
(c) Pentose indicates a five-carbon
carbohydrate; also indicates an aldehyde group
(on carbon 1); D- indicates that the OH on carbon 4
(adjacent to the terminal CH2OH) is on the right.
The orientation of the OH groups on carbons 2 and
3 is not specified here and therefore can be
written in either direction for this problem:
IMPORTANCE OF CARBOHYDRATES
1. Used by essentially all cells as an energy source
- glycolysis: metabolic machinery to oxidize
carbohydrates to smaller carboxylic acids
- mitochondria: plant and animal cells, spe-
cialize in carbon oxidation
In eukaryotic cells (including human cells), carbons
from carbohydrate can be completely oxidized to
carbon dioxide.
2. Easily transported between and within cells
- glucose: carried in the bloodstream from cell
to cell
- disaccharide lactose: mammals, dissolved in
milk, to transport carbohydrates from mother to
baby
- sucrose: higher plants, transport carbohydrate
3. Provide essential structural support for both
plant and animal cells
- large polymers (polysaccharides) with
important structural characteristics can be formed
from simple sugars
- carbohydrate polymers found in animal
connective tissue. (e.g. provide the cushion that
allows our joints to move smoothly)
- cellulose: part of the cell wall for all higher
plants, an effective structural polymer, flexible,
comfortable cotton clothing; and disposable,
biodegradable paper products
MONOSSACHARIDE
- Pentose monosaccharide (ribose) and its
deoxy derivative: essential components of RNA
and DNA
- Hexose monosaccharides: most important
carbohydrate sources of cellular energy
Three hexoses—glucose, galactose, and fructose—
are of major significance in nutrition.
In humans, the liver coordinates carbohydrate
metabolism. This organ monitors the flow
of blood from the small intestine and removes the
digested carbohydrates. Most of
these molecules are then converted to glucose and
may be stored. In response to
hormones such as insulin and glucagon, the liver
works to maintain normal blood
sugar levels by either releasing or absorbing
glucose. This sugar plays a central role
in carbohydrate metabolism.
 Projection Formulas
a. Glucose
1. Fischer Projection
- most important of the monosaccharides 2. Howarth Projection
- most abundant carbohydrate in the blood
- an aldohexose, found in the free state in plant Emil Hermann Fischer: established the structural
and animal tissue configuration of glucose
- also known as dextrose (dextrorotatory) or grape
sugar (occurs in grapes) Projection formula: commonly written in either of
- component of the disaccharides sucrose, two ways, with or without the chiral carbon atoms.
maltose, and lactose, monomer of the
polysaccharides starch, cellulose, and glycogen
- intermediate sweetness
- glycosuria: the condition in which glucose is
excreted in the urine

* The concentration of glucose in the blood is

normally 80–100 mg per 100 mL of blood.

b. Galactose

- aldohexose
- occurs in pectin, gums, and mucilages
- isomer of glucose
- synthesized in the mammary glands
- constituent of glycolipids
- is less than half as sweet as glucose
- galactosemia: the inability of infants to
metabolize galactose

c. Fructose

- also known as levulose

- ketohexose that occurs in fruit juices and honey Epimers: any two monosaccharides that differ only
- constituent of sucrose in the configuration around a single carbon atom.
- major constituent of the polysaccharide inulin Thus, D- and L-glyceraldehyde are
- the sweetest epimers.
Kiliani–Fischer synthesis: the laboratory
conversion of one aldose into another aldose
containing one more carbon atom
Heinrich Kiliani (1855–1945) discovered that the
addition of HCN to an aldose formed a
cyanohydrin.
The Kiliani–Fischer synthesis involves
(1) the addition of HCN to form a cyanohydrin;
(2) hydrolysis of the CN group to
COOH; and
(3) reduction with sodium amalgam, Na(Hg), to
form the aldehyde.
MUTAROTATION
Pyranose - structure that includes a six-membered
ring consisting of five carbon atoms and one
oxygen atom
Two cyclic forms differ with respect to their
rotation of polarized light:
1. a-D-glucopyranose (+112 degrees)
2. b-D-glucopyranose (+18.7 degrees)
Mutarotation
An interesting phenomenon occurs when these
two forms of glucose are put into
separate solutions and allowed to stand for several
hours. The specific rotation of
each solution changes to 52.7°.
D-glucose exists in solution as an equilibrium
mixture of two cyclic forms and the open-chain
form.
Equilibrium solution contains about 36% a
molecules and 64% b molecules.
Anomers: when two cyclic isomers differ only in
their stereo arrangement about the carbon
involved in mutarotation; exists only in cyclic
monosaccharides
EXAMPLES
Write the pyranose Haworth perspective formulas
and names for the two anomers of
D-mannose.
First, write the open-chain Fischer projection
formula for D-mannose:
Next, draw the structure of the Haworth pyranose
ring. Placing the CH2OH (C-6) group in the up
position on the ring. Then, refer to the open-chain
Fischer projection formula.
 All the hydroxyl groups on the right of the open
chain should be written down in the Haworth
formula, and all the hydroxyl groups on the left
should be written up. Since this rule only applies
to chiral centers, we can ignore the hydroxyl on
carbon 6:
The carbon involved in mutarotation, carbon 1,
can have either of two configurations, the a
anomer when the hydroxyl is pointed down or the
b anomer when pointed up.
The last step is to add the hydroxyl group at
carbon 1 and name the anomers:
HEMIACETALS AND ACETALS
Hemiacetal structure consists of an ether linkage
and an alcohol linkage on the same carbon atom
(shown in red), whereas the acetal structure has
two ether linkages to the same carbon atom:
Cyclic structures of monosaccharides are
intramolecular hemiacetals. Five- or six-
membered rings are especially stable:
When an alcohol, ROH, reacts with another
alcohol, R'OH, to split out H2O, the
product formed is an ether, ROR'.
Glycoside. When a monosaccharide hemiacetal
reacts with an alcohol, the product is an acetal.
In carbohydrate terminology, this acetal structure
is called a glycoside (derived from
the Greek word glykys, meaning “sweet”). In the
case of glucose, it would be a glucoside;
if galactose, a galactoside; and so on.
example:
Heart stimulants such as digi-
talis and ouabain are known as heart glycosides.
Several antibiotics such as streptomycin and
erythromycin are also glycosides.
STRUCTURES OF GALACTOSE AND FRUCTOSE
Galactose vs Glucose
Galactose, like glucose, is an aldohexose and
differs structurally from glucose only in
the configuration of the H and OH group on carbon
4:
Fructose is a ketohexose. The open-chain form
may be represented in a Fischer
projection formula:
Like glucose and galactose, fructose exists almost
entirely in cyclic forms. One common cyclic
structure is a five-membered ring containing
oxygen. This is termed a
furanose ring by comparison with the organic
molecule, furan.
PENTOSES
An open-chain aldopentose has three chiral
carbon atoms.
Arabinose and xylose occur in some plants as
polysaccharides called pentosans.
D-Ribose and its derivative, D-2-deoxyribose, are
the most interesting pentoses be-
cause of their relationship to nucleic acids and the
genetic code.
*2-deoxy means that oxygen is missing from the D-
ribose molecule at carbon 2.
The ketose that is closely related to D-ribose is
named D-ribulose. (Ketose names are
often derived from the corresponding aldose name
by changing the suffix from -ose to -ulose.) This
ketose is an intermediate that allows cells to make
many other monosaccharides. In photosynthetic
organisms, it is used to capture carbon dioxide
and thus make new carbohydrates.
DISSACHARIDES large intestine. The gas and intestinal discomfort
that results is termed milk or lactose intolerance
- carbohydrates composed of two monosaccharide and is a condition that afflicts many adults.
residues united by a glycosidic linkage.
- The two important disaccharides: sucrose and STRUCTURES AND PROPERTIES OF DISACCHARIDES
lactose (C12H22O11)
- Sucrose: table sugar, exists throughout the a-D-glucopyranosyl-(1,4)-a-D-glucopyranose
plant kingdom. Sugar cane contains 15–20%
sucrose, and sugar beets 10–17%. Maple syrup
and sorghum are also good sources of sucrose.
- Lactose: milk sugar, found free in nature,
mainly in the milk of mammals. Human milk
contains about 6.7% lactose and cow milk about
4.5% lactose.

Unlike sucrose and lactose, several other

disaccharides are derived directly from
polysaccharides by hydrolysis. For example,
maltose, isomaltose, and cellobiose are formed
when specific polysaccharides are hydrolyzed.
Maltose is the most common and is found as a
constituent of sprouting grain. Two conventions are used for writing Haworth
formulas connecting two or more
Hydrolysis: disaccharides yield two monosaccharide units through a glycoside bond.
monosaccharide molecules; catalyzed by hydrogen
ions (acids) or by enzymes that act effectively at First convention for lactose,for example, we find
room or body temperatures. that the glycosidic bond is shown in a bent fashion
to provide stereochemical information:
A different enzyme is required for the hydrolysis of
the three disaccharides:

The bond from carbon 1 in galactose is the b

configuration pointing up and is bonded through
oxygen to carbon 4 of glucose, whose bond to
oxygen points down.

The enzyme lactase is present in the small

intestine of infants and allows them to easily
digest lactose from their milk diet. Unfortunately,
as people mature their intestines often stop
producing the lactase enzyme, and they lose the
ability to digest lactose. Instead, this sugar is
metabolized by common bacteria that live in the
Second convention: two monosaccharides are
shown in a “stacked” position. In lactose, the
glycosidic bond from carbon 1 of galactose in the b
position is pointed up and is directly bonded
through oxygen to carbon 4 of glucose,whose bond
to oxygen is pointed down. These two conventions
are illustrated as follows:
Sucrose consists of an b-D-glucopyranose unit and
a b-D-fructofuranose unit. These monosaccharides
are joined by an oxygen bridge from carbon 1 on
glucose to carbon 2 on fructose—that is, by an b-
1,2-glycosidic linkage:
Fructose is bonded to glucose through the b-2
position of fructose to the a-1 position of glucose.
EXAMPLES
Write the Haworth formula for isomaltose, which
is a-D-glucopyranosyl-(1,6)-a-D-glucopyranose.
Recognize that this disaccharide is composed of
two a-D-glucopyranose units linked between
carbon 6 of one unit and carbon 1 of the other.
First, write the Haworth formula for the
monosaccharides, and number their carbons:
The two a-D-glucopyranose units must be linked in
such a way that the stereochemistry at carbon 1 is
preserved. (Carbon 6 is not a chiral center.)
One correct way to write the isomaltose structure
is as follows:
Sucrose vs Lactose vs Maltose
Lactose and maltose both show mutarotation.
Sucrose has no hemiacetal structure and hence
does not mutarotate.
The three disaccharides have physical properties
associated with large polar molecules. All three
are crystalline solids and are quite soluble in
water.
Solubility of sucrose amounts to 200 g per 100 g of
water at 0°C.
Major factor in this high solubility: Hydrogen
bonding between the polar OH groups on the
sugar molecules and the water molecules.
These sugars are not easily melted. In fact, lactose
is the only one with a clearly defined melting point
(201.6°C).
Sucrose and maltose begin to decompose when
heated to 186°C and 103°C.
*When sucrose is heated to melting, it darkens and
undergoes partial decomposition. The resulting
mixture, known as caramel or burnt sugar, is used
as coloring as well as a flavoring agent in foods.
SWEETENERS AND DIET
Fructose: sweetest
Sucrose (table sugar): most commonly used
sweetener, 58% as sweet as fructose
Sucrose has a tendency to crystallize from
concentrated solutions or syrups. There-
fore, in commercial food preparations (e.g.,
candies, jellies, and canned fruits) the sucrose is
often hydrolyzed.
The resulting mixture of glucose and fructose is
called invert sugar. Invert sugar has less tendency
to crystallize than sucrose, and it has greater
sweetening power than an equivalent amount of
sucrose.
High-fructose syrups, derived from cornstarch, are
used as sweeteners in products
such as soft drinks.
Starch is a polymer of glucose, contains no
fructose, and is not sweet.
However, through biotechnology, a method was
developed to convert starch to a very
sweet syrup of high fructose content.
The starch polymers are hydrolyzed to glucose;
then part of the glucose is enzymatically
converted to fructose, yielding the syrup.
HEALTH PROBLEMS
Sucrose: calories, oral bacteria
Fructose and glucose: quickly absorbed from the
small intestine, sugar consumption leads to a rapid
increase in blood sugar. Such a sharp rise can be
dangerous for people with impaired carbohydrate
metabolism—for example, those who have
diabetes mellitus.
Saccharin, which was discovered in 1879, was the
first purely artificial, noncarbohydrate sweetener.
In 2002, neotame was approved by the
FDA. This molecule is related to aspartame.
REDOX REACTIONS OF MONOSACCHARIDES

Two common metabolic processes

First, glycolysis is found in almost all cells. It starts

with glucose and forms two small carboxylic acids.
The aldehyde functional group of glucose, where
the carbon has two bonds to oxygen, is converted
to a carboxylic acid, where the carbon has three
bonds to oxygen; carbon oxidation has occurred Dilute nitric acid, a vigorous oxidizing agent,
and energy is released. oxidizes both carbon 1 and carbon 6 of
aldohexoses to form dicarboxylic acids. The
resulting acid is named by changing the -ose sugar
suffix to -aric acid. Glucose yields glucaric acid
(saccharic acid) and galactose yields galactaric acid
(mucic acid):
Second, the citric acid cycle is found in the
mitochondria. The carboxylic acids formed in
glycolysis are converted to carbon dioxide. Every
carbon from glucose ends in a molecule of CO2
with four bonds to oxygen. Glucose is completely
oxidized, and a maximum energy is released. In
fact, the citric acid cycle releases about 10 times
the energy released during glycolysis.

OXIDATION
*Notice that galactaric acid is a meso compound:
It is superimposable on its mirror image.
Carbohydrate oxidation increases the number of
bonds between carbon and oxygen.
REDUCTION

The aldehyde groups in monosaccharides can be

Carbohydrate reduction decreases the number of
oxidized to monocarboxylic acids by mild oxidizing
bonds between carbon and oxygen.
agents such as bromine water.

Monosaccharides can be reduced to their

The carboxylic acid group is formed at carbon 1.
corresponding polyhydroxy alcohols by reducing
The name of the resulting acid is formed by
agents such as H2/Pt or sodium amalgam, Na(Hg).
changing the -ose ending to -onic acid. Glucose
yields gluconic acid, galactose yields galactonic
acid, and so on.
For example, glucose yields sorbitol (glucitol),
galactose yields galactitol (dulcitol), and mannose
yields mannitol; all of these are hexahydric
alcohols (containing six OH groups).

DEFINITION OF TERMS and TO REMEMBER

Aldehyde vs Ketones
Aldehyde contains the group —CHO
Ketone contains a carbonyl group =C=O
Ketotriose. the only sugar that doesn't have any
enantiomer

Enantiomer vs Epimer
e.g. Enantiomer
a-D-Glucopyranose and a-L-Glucopyranose
e.g. Epimer
a-D-Glucopyranose and a-D-Galactopyranose

Epimer. each of two isomers with different

configurations of atoms around one of several
asymmetric carbon atoms present