Chapter Thre

Amino Acids an
Peptide

Paul D. Adams • University of Arkansas

cengage.com/chemistry/campbell
Chapter Outline
3-1 Amino Acids Exist in a 3-D World

3-2 Individual Amino Acids: Their Structures and

Properties

3-3 Amino Acids Can Act as Both Acids and Bases

3-4 The Peptide Bond

3-5 Small Peptides with Physiological Activity

Amino Acids Exist in a 3-D World
• Amino acid: a compound that contains
both an amino group and a carboxyl
group
• -Amino acid has an amino group
attached to the carbon adjacent to
the carboxyl group
• -carbon also bound to side chain
group, R
• R gives identity to amino acid
• Two steroisomers of amino acids
are designated L- or D-.
Based on similarity to
glyceraldehdye (Figure 3.2)
Amino Acid Structure and Properties
• With the exception of glycine, all protein-derived
amino acids have at least one stereocenter (the -
carbon) and are chiral (stereoisomers)
• the vast majority of -amino acids have the L-
configuration at the -carbon (Proline is usually D)
• Side-chain carbons in other amino acids designated
with Greek symbols, starting at a carbon (…etc)
• Amino acids can be referred to by three-letter or one-
letter codes. Table 3.1 (KNOW THESE)
Individual Amino Acids
• Group A: Nonpolar side chains- Ala, Val, Leu, Ile,
Pro. Phe, Trp, Met
• Ala, Val, Leu, Ile, Pro- contain aliphatic hydrocarbon
group. Pro has cyclic structure
• Phe- hydrocarbon aromatic ring
• Trp- Indole ring side chain, aromatic
• Met- Sulfur atom in side chain
Amino Acids (cont’d)
• Group B: Neutral Polar side chains- Ser, Thr, Tyr,
Cys, Glu, Asn

• Ser, Thr- Side chain is polar hydroxyl group

• Tyr- hydroxyl group bonded to aromatic hydrocarbon

group

• Cys- Side chain contains thiol group (-SH)

• Gln, Asn- contain amide bonds in side chain

Amino Acids (cont’d)
• Group C: Acidic Side Chains: Glu, Asp

• Both have a carboxyl group in side chain

• Can lose a proton, forming a carboxylate ion

• These amino acids are negatively charged at neutral

pH
Amino Acids (cont’d)
• Group D: Basic side chains: His, Lys, Arg

• Side chains are positively charged at pH 7

• Arg-side chain is a guanidino group

• His-side chain is an imidazole group

• Lys-side chain NH3 group is attached to an aliphatic

hydrocarbon chain
Acidity: -COOH Groups
• The average pKa of an -carboxyl group is 2.19,
which makes them considerably stronger acids than
acetic acid (pKa 4.76)

• the greater acidity of the amino acid carboxyl group is

due to the electron-withdrawing inductive effect of the
-NH3+ group
Basicity
• -NH3+ groups: The average value of pKa for an -NH3+ group
is 9.47, compared with a value of 10.76 for a 2°
alkylammonium ion
Guanidine Group
• The side chain of arginine is a considerably stronger base
than an aliphatic amine
• basicity of the guanido group is attributed to the large
resonance stabilization of the protonated form relative to
the neutral form

Imidazole Group
• The side chain imidazole group of histidine is a
heterocyclic aromatic amine
Amino acid summary
Important structural features:

1. All 20 are -amino acids

2. For 19 of the 20, the -amino group is primary; for proline,

it is secondary

3. With the exception of glycine, the a-carbon of each is a

stereocenter

4. Isoleucine and threonine contain a second stereocenter

5. 3, and 1-letter codes in Table 3.1.

Uncommon Amino Acids
• Each derived from
a common amino
acid by a
modification
• hydroxylysine and
hydroxyproline are
found only in a
few connective
tissues such as
collagen
• thyroxine is found
only in the thyroid
gland
Ionization of Amino Acids
• Remember, amino acids without charged groups on side chain
exist in neutral solution as zwitterions with no net charge
Titration of Amino Acids
• When an amino acid is titrated, the titration curve represents the reaction of
each functional group with the hydroxide ion
Titration of histidine with NaOH
Ionization of Amino Acids
• In amino acid,
carboxyl group (-)
and amino group
(+) are charged at
neutral pH.
• In free amino
acids -carboxyl,
and a-amino
groups have
titratable protons.
Some side chains
do as well
Isoelectric pH
• Isoelectric pH, pI: the pH at which the majority of molecules
of a compound in solution have no net charge

• the pI for glycine, for example, falls midway between the pKa
values for the carboxyl and amino groups

• Isoelectric pH values for the 20 protein-derived amino acids are

given in Table 3.2
The Peptide Bond
• Individual amino acids
can be linked by forming
covalent bonds.
• Peptide bond: the
special name given to
the amide bond between
the -carboxyl group of
one amino acid and the
-amino group of
another amino acid
Direction of Peptide Chain
Geometry of Peptide Bond
• the four atoms of a peptide bond and the two alpha
carbons joined to it lie in a plane with bond angles of
120°about C and N
• to account for this geometry, a peptide bond is most
accurately represented as a hybrid of two contributing
structures (resonance structures)
• the hybrid has considerable C-N double bond
character and rotation about the peptide bond is
restricted
Resonance Structures of Peptide Bond
Small Peptides with Physiological Activity