Bettelheim / Brown / Campbell / Farrell / Torres

Introduction to General, Organic, and Biochemistry 11e

BIOCHEMISTR
Y
William H. Brown Beloit College www.cengage.com/chemistry/bettelheim
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 AUF Prayer
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We, the AUF Community,
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For Your greater Glory.
Cyclic Structure of Monosaccharides
• Aldehydes and ketones react with alcohols to form
hemiacetals
• Ability of their carbonyl group to react intramolecularly
with hydroxyl group and results to a cyclic hemiacetal
• Cyclic hemiacetals form readily when hydroxyl and
carbonyl groups are part of the same molecule and
their interaction can form a five- or six-membered ring.

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Haworth Projections
• A common way of
representing the cyclic
structure of
monosaccharides
• Named after the English
chemist Sir Walter N.
Haworth

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Haworth Projections
D-Glucose (C6H12O6) forms these two cyclic hemiacetals.
-2 dimensional structural notation that specifies the 3d
structure of a cyclic form of monosaccharides

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Haworth Projections
• A five- or six-membered cyclic hemiacetal is
represented as a planar pentagon or hexagon,
lying roughly perpendicular to the plane of
the paper.
• Groups bonded to the carbons of the ring then
lie either above or below the plane of the ring.
• The new carbon stereocenter created in
forming the cyclic structure is called the
anomeric carbon.
• Stereoisomers that differ in configuration only
at the anomeric carbon are called anomers.
• The anomeric carbon of an aldose is C-1; that
of the most common ketose is C-2. 8
Haworth Projections
In the terminology of carbohydrate chemistry (2 Forms of
Stereoisomerism),
•  means that the -OH on the anomeric carbon is on the
same side of the ring as the terminal -CH2OH.
•  means that the -OH on the anomeric carbon is on the
side of the ring opposite from the terminal -CH2OH.
• A six-membered hemiacetal ring is called a pyranose,
and a five-membered hemiacetal ring is called a
furanose because these ring sizes correspond to the
heterocyclic compounds furan and pyran.

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10
Cyclic Structure of Monosaccharides
• Aldehydes and ketones react with alcohols to form
hemiacetals
• Ability of their carbonyl group to react intramolecularly
with hydroxyl group and results to a cyclic hemiacetal
• Cyclic hemiacetals form readily when hydroxyl and
carbonyl groups are part of the same molecule and
their interaction can form a five- or six-membered ring.

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Haworth Projections
• Aldopentoses also form cyclic hemiacetals.
• The most prevalent forms of D-ribose and other
pentoses in the biological world are furanoses.

• The prefix “deoxy” means “without oxygen.”

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Haworth Projections
D-Fructose (a 2-ketohexose) also forms a five-membered
cyclic hemiacetal.

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Chair Conformations
• For pyranoses, the six-membered ring is more accurately
represented as a strain-free chair conformation.

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Chair Conformations
• In both Haworth projections and chair conformations, the
orientations of groups on carbons 1- 5 of -D-
glucopyranose are up, down, up, down, and up and all are
equatorial.

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Mutarotation
• Mutarotation: The change in specific rotation that
accompanies the equilibration of - and -anomers in
aqueous solution.
• Example: When either -D-glucose or -D-glucose is
dissolved in water, the specific rotation of the solution
gradually changes to an equilibrium value of +52.7°,
which corresponds to 64% beta and 36% alpha forms.

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18
midterms

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 Characteristic Reactions of
Monosaccharides:
• A. Formation of Glycosides (Acetals)
• B. Reduction to Alditols
• C. Oxidation to Aldonic Acid
(Reducing Sugars)
• D. Oxidation to Uronic
Acids
• E. Formation of Phosphoric
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Characteristic Reactions of Monosaccharides:

• A. Formation of Glycosides (Acetals)

Treatment of an Aldehyde or a Ketone
with one molecule of alcohol yields a
hemiacetal
Treatment of the hemiacetal with a
molecule of alcohol yields an acetal

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Formation of Glycosides
• Treatment of a monosaccharide, all of which exist almost
exclusively in cyclic hemiacetal forms, with an alcohol
gives an acetal. Reaction of β-D-glucopyranose with
methanol

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Formation of Glycosides
• A cyclic acetal derived from a monosaccharide
is called a glycoside (general name for
monosaccharide acetals)
• Glycoside- Cyclic monosaccharide by
replacement of the hemiacetal carbon –OH
group with an –OR group
• GLUCOSIDE- Glycoside produced from
glucose
• The bond from the anomeric carbon to the -OR
group is called a glycosidic bond.

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Naming glycosides

• Glycosides are stable in water and

aqueous base, but like other acetals, are
hydrolyzed in aqueous acid to an alcohol
and a monosaccharide.
• Glycosides are named by listing the alkyl
or aryl group bonded to oxygen followed
by the name of the carbohydrate in
which the ending -e is replaced by -ide.

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Continuous-Chain Alkanes
Alkyl Group
• Group of atoms that would be
obtained by removing a hydrogen
atom from an alkane
• Substituents
• Ex. 2-methylpentane
• Alkane CH4
• Alkyl CH3
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Table 2. Names for the First Six Continuous-Chain Alkyl Groups

Num Structural Formula IUPAC Suffix Alkyl

ber of Prefix Group
C Nam
e
1 CH3— meth- -yl methyl
2 CH3-CH2— eth- -yl ethyl

3 CH3-CH2-CH2— prop- -yl propyl

4 CH3-CH2-CH2-CH2— but- -yl butyl
5 CH3-CH2-CH2-CH2- pent- -yl pentyl
CH2—
6 CH3-CH2-CH2-CH2- hex- -yl hexyl
CH2-CH2— Copyright © Cengage Learning.
• Glycosides are named by listing the alkyl or
aryl group bonded to oxygen followed by
the name of the carbohydrate in which the
ending -e is replaced by -ide.
• Ex.
• Methyl glycoside derived from β-D-glucopyranose is named
• Methyl-β-D-glucopyranoside

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Cyclic Hemiacetal Forms of D-Glucose
6 6
CH2OH CH2OH

O O O
5 5 H
4 1
O 4 O
1
H 2 O
H 2
O O
H 3 H H 3
OH OH
-D-Glucose -D-
Glucose

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Draw a structural formula for methyl β-D-
riboside. Label the anomeric carbon
and the glycosidic bond.

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 Characteristic Reactions of
Monosaccharides:
• A. Formation of Glycosides (Acetals)
• B. Reduction to Alditols
• C. Oxidation to Aldonic Acid
(Reducing Sugars)
• D. Oxidation to Uronic
Acids
• E. Formation of Phosphoric
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Reduction to Alditols
• The carbonyl group of a monosaccharide
can be reduced to a hydroxyl group by a
variety of reducing agents, including NaBH4
(sodium borohydride) and H2 in the
presence of a transition metal catalyst
(H2/Pt).
• The reduction product is called an alditol.
• Alditols are named by changing the suffix
-ose to -itol.

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Reduction to Alditols
• D-Glucose (open chain form)
• Small amount of this form is present in
solution but as it is reduced, the
equilibrium between cyclic hemiacetal
forms

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ARTIFICIAL SWEETENERS

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• Sorbitol is found in the plant world in many
berries and in cherries, plums, pears, apples,
seaweed, and algae.
• It is about 60 percent as sweet as sucrose
(table sugar) and is used in the manufacture of
candies and as a sugar substitute for diabetics.
• These three alditols are also common in the
biological world. Note that only one of these is
chiral.`

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Aldehydes and Ketones
• Aldehydes are the intermediate products
in the oxidation (for organic compounds, a
carbon atom is oxidized if it loses
hydrogen atoms or gains oxygen atoms in
a chemical reaction) of primary alcohols
• Aldehydes: Carbonyl is attached to at least
one H atom in aldehydes
• Aldehydes have the formula R-CHO
O O

C C
K e t o n e
H F u n c t i o n a l G r o u p
Copyright © Cengage Learning.
A l d e h y d e
• Ketones: Carbonyl is directly attached
with two carbon atoms in ketones
• Ketones are the products of oxidation
of secondary alcohols
• Ketones R-CO-R
O O

C C
Ketone
H Functional
Aldehyde Group
Copyright © Cengage Learning.
 Characteristic Reactions of
Monosaccharides:
• A. Formation of Glycosides (Acetals)
• B. Reduction to Alditols
• C. Oxidation to Aldonic Acid
(Reducing Sugars)
• D. Oxidation to Uronic
Acids
• E. Formation of Phosphoric
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Oxidation to Aldonic Acids (Reducing Sugars)
• Aldehydes are oxidized to carboxylic acids by several
agents, including oxygen
• The aldehyde group of an aldose is oxidized
under basic conditions to a carboxylate group.
• The cyclic form of the aldose is in equilibrium
with the open-chain form, which is then oxidized
by the mild oxidizing agent.
• The oxidation product is called an aldonic
acid.
• A carbohydrate that reacts with an oxidizing
agent to form an aldonic acid is classified as a
reducing sugar (it reduces the oxidizing agent).
• sugars.
2-Ketoses (e.g. D-fructose) are also reducing 40
Oxidation to Aldonic Acids

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 Characteristic Reactions of
Monosaccharides:
• A. Formation of Glycosides (Acetals)
• B. Reduction to Alditols
• C. Oxidation to Aldonic Acid
(Reducing Sugars)
• D. Oxidation to Uronic
Acids
• E. Formation of Phosphoric
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D. Oxidation to Uronic Acid
• Oxidation of sugars in nature is catalyzed
by enzymes
• Enzyme catalyzed oxidation of D-glucose
yields D-glucuronic acid
• In biochemical systems enzymes can
oxidize the primary alcohol end of an
aldose such as glucose, without oxidation
of the aldehyde group, to produce an
alduronic acid.
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D-Glucuronic Acid
• The body uses glucuronic acid to detoxify foreign alcohols
and phenols.
• These compounds are converted in the liver to glycosides
of glucuronic acid and then excreted in the urine.
• The intravenous anesthetic Propofol is converted to the
following water-soluble glucuronide and excreted.

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 Characteristic Reactions of
Monosaccharides:
• A. Formation of Glycosides (Acetals)
• B. Reduction to Alditols
• C. Oxidation to Aldonic Acid
(Reducing Sugars)
• D. Oxidation to Uronic
Acids
• E. Formation of Phosphoric
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Phosphate Ester Formation
• Formation of Phosphoric Esters
• Glycolysis- conversion of glucose to glucose 6-
phosphate
• Phosphoric acid is strong enough that at the pH of
cellular and intercellular fluids, both acidic
protons of the phosphoric ester are ionized,
giving the ester a charge of -2
• Phosphate ester formation: The hydroxyl groups
of a monosaccharide can react with inorganic
oxyacids to form inorganic esters.
• Phosphate esters of various monosaccharides are
stable in aqueous solution and play important
roles in the metabolism of carbohydrates .
C opyright © Cengage
48
 What are
Disaccharides and

Oligosaccharides?
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• Disaccharides
• Contain two units monosaccharides
• Joined by a glycosidic bond between
the anomeric carbon of one unit and an
–OH group of the other unit
• Trisaccharides
• Contains three units monosaccharides
• Oligosaccharides
• contain six to ten monosaccharide 50
Three important disaccharides
• Sucrose
• Lactose
• maltose

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Sucrose- most abundant
• Table sugar, obtained from the juice of sugar cane and
sugar beet.

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Sucrose
• Nonreducing sugar
• No hemiacetal is present in the molecule
• Glycosidic linkage involves the reducing
ends of both monosaccharides
• Open chain form is not possible
• Two monosaccharide units present: α-D-
glucose and β-D-fructose
• Enzyme needed to break the linkage in
sucrose: SUCRASE (present in human body)
• Sucrose is an easily digested substance
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Lactose
• The principal sugar present in milk.
• About 5 - 8% in human milk, 4 - 5% in
cow’s milk.

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Lactose
• Reducing sugar
• Cyclic hemiacetal of the D-
glucopyranose unit is in equilibrium
with its open-chain form and can be
oxidized to a carboxyl group
• Lactose is made up of: β-D-galactose
unit and D-glucose unit joined by a
β(1-4) glycosidic linkage
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Maltose (Malt Sugar)
• From malt, the juice of sprouted barley and
other cereal grains.

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Maltose (Malt Sugar)
• Consists of 2 D-glucose units, one of
which must be α–D-glucose; joined by a
glycosidic bond between carbon 1
(anomeric carbon) of one unit and carbon
4 of the other unit; the bond is an α-1,4-
glycosidic bond
• Reducing sugar- hemiacetal group on the
right unit of D-glucopyranose is in
equilibrium with the free aldehyde and
can be oxidized to a carboxylic acid 60
 WHAT ARE
POLYSACCHARIDES?

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Polysaccharides
Polysaccharide: A carbohydrate
consisting of large numbers of
monosaccharide units joined by
glycosidic bonds.

STARCH
GLYCOGEN
CELLULOSE 62
Starch: A polymer of D-glucose.
• Starch can be separated into amylose
and amylopectin.
• Amylose is composed of unbranched
chains of up to 4000 D-glucose units
joined by -1,4-glycosidic bonds.
• Amylopectin contains chains up to 10,000
D-glucose units also joined by -1,4-
glycosidic bonds. At branch points, new
chains of 24 to 30 units are started by -
1,6-glycosidic bonds. 63
Polysaccharides
• Figure 20-3 Amylopectin is a branched polymer of D-
glucose units joined by -1,4-glycosidic bonds. Branches
consist of D-glucose units that start with an -1,6-
glycosidic bond.

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Polysaccharides
• Glycogen is the energy-reserve
carbohydrate for animals.
• Glycogen is a branched polysaccharide
of approximately 106 glucose units joined
by -1,4- and -1,6-glycosidic
bonds.
• The total amount of glycogen in the body
of a well-nourished adult human is
about 350 g, divided almost equally
between liver and muscle.
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Polysaccharides
Cellulose is a linear polysaccharide of D-glucose units
joined by -1,4-glycosidic bonds.
• It has an average molecular weight of 400,000 g/mol,
corresponding to approximately 2200 glucose units per
molecule.
• Cellulose molecules act like stiff rods and align
themselves side by side into well-organized
water-insoluble fibers in which their -OH
groups form
numerous intermolecular hydrogen bonds.
• This arrangement of parallel chains in bundles gives
cellulose fibers their high mechanical strength.
• It is also the reason why cellulose is insoluble in
water.

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Polysaccharides
• Figure 20-4 Cellulose is a linear polysaccharide of
D- glucose units joined by -1,4-glycosidic bonds.

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Polysaccharides
Cellulose (cont’d)
• Humans and other animals can not digest cellulose
because their digestive systems do not contain
-glycosidases, enzymes that catalyze the
hydrolysis
of -glycosidic bonds.
• Termites have such bacteria in their intestines and can
use wood as their principal food.
• Ruminants (cud-chewing animals) and horses can
also
digest grasses and hay.
• Humans have only -glucosidases; hence, the
polysaccharides we use as sources of glucose are
starch and glycogen.
• Many bacteria and microorganisms have
-glucosidases. 68
Acidic Polysaccharides
Acidic polysaccharides: a group of polysaccharides that
contain carboxyl groups and/or sulfuric ester groups, and
play important roles in the structure and function of
connective tissues.
• There is no single general type of connective tissue.
• Rather, there are a large number of highly specialized
forms, such as cartilage, bone, synovial fluid, skin,
tendons, blood vessels, intervertebral disks, and
cornea.
• Most connective tissues are made up of collagen, a
structural protein, in combination with a variety of
acidic polysaccharides.

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Acidic Polysaccharides
Heparin (cont’d)
• Heparin is synthesized and stored in mast cells of
various tissues, particularly the liver, lungs, and gut.
• The best known and understood of its biological
functions is its anticoagulant activity.
• It binds strongly to antithrombin III, a plasma
protein involved in terminating the clotting process.

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Heparin
• Figure 20-5 The repeating pentasaccharide unit of
heparin.

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Chapter 20 Carbohydrates

End
Chapter 20

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