Peptides and

Polypeptides
“Peptides”
Short polymers of amino acids
Each unit is called a residue
2 residues - dipeptide
3 residues - tripeptide
12-20 residues - oligopeptide
many - polypeptide
Peptide Bond
Usually found in the trans conformation
Has partial (40%) double bond character
About 0.133 nm long - shorter than a typical single bond but longer
than a double bond
Due to the double bond character, the six atoms of the peptide bond
group are always planar!
N partially positive; O partially negative
• Peptide bonds are strong and not broken by
conditions that denature proteins, such as
heating.
• Prolonged exposure to a strong acid or base at
elevated temperatures is required to hydrolyse
these bonds non-enzymically.
Characteristics of Peptide Bonds
Has a partial double-bond character
◦ Shorter than a single bond
◦ Rigid and Planar

Prevents free rotation around the bond between the carbonyl carbon
and the nitrogen of the peptide bond.
The bonds between the α-carbons and the α-amino or α-carboxyl
groups can be freely rotated
◦ Allows the polypeptide chain to assume a variety of possible configurations.
Nature of Peptide Bonds
Rotation around C-N bond is restricted due to the double-
bond nature of the resonance hybrid form
Peptide groups are therefore planar
Six atoms lie in the same plane
◦ α-carbon atom and CO group from the first amino acid
◦ NH group and α-carbon atom from the second amino acid.
Six atoms of the peptide group lie in a
plane!
Configuration
Two configurations are possible for a planar peptide
bond
◦ In the trans configuration, the two α-carbon atoms are on opposite
sides of the peptide bond
◦ In the cis configuration, these groups are on the same side of the
peptide bond.

Almost all peptide bonds in proteins are trans.

Polypeptides are long chains of amino acids linked by
peptide bonds

Proteins are made up of one or more polypeptide chains .

Free amino end of the peptide chain (N-terminal) is written to the
left and the free carboxyl end (C-terminal) to the right
All amino acid sequences are read from the N- to the C-terminal end
of the peptide.
Linkage of many amino acids through peptide bonds results in an
unbranched chain called a polypeptide.
Peptides made of small numbers of amino acids (<10) are
called oligopeptides or peptides
Chains that are between 10-50 amino acids are referred to
as polypeptide
•Polypeptides (covalently linked -amino acids) + possibly:
• cofactors
 functional non-amino acid component
 metal ions or organic molecules

• coenzymes
 organic cofactors
 NAD+ in lactate dehydrogenase

• prosthetic groups
 covalently attached cofactors
 heme in myoglobin

• other modifications