aminoácidos, petidios e proteinas ch23mr
TRANSCRIPT
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Organic Chemistry 4th Edition
Paula Yurkanis Bruice
Chapter 23
Amino Acids,Peptides,
and Proteins
Irene LeeCase Western Reserve
UniversityCleveland, OH
©2004, Prentice Hall
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Peptides and proteins are polymers of amino acids linkedtogether by amide bonds
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Aliphatic Side-Chain Amino Acids
+H3N CH C
H
O-
O
+H3N CH C
CH3
O-
O
+H3N CH C
CH
O-
O
CH3
CH3
+H3N CH C
CH2
O-
O
CH CH3
CH3
+H3N CH C
CH
O-
O
CH3
CH2
CH3
glycine alanine
valine leucine isoleucine
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Hydroxy-Containing Amino Acids
Sulfur-Containing Amino Acids
+H3N CH C
CH
O-
O
OH
CH3
+H3N CH C
CH2
O-
O
OH
serine threonine
+H3N CH C
CH2
O-
O
SH
+H3N CH C
CH2
O-
O
CH2
S
CH3cysteine methionine
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Acidic Amino Acids
Amides of Acidic Amino Acids
+H3N CH C
CH2
O-
O
C
O-
O
+H3N CH C
CH2
O-
O
CH2
C
O-
Oaspartatic acid glutamic acid
+H3N CH C
CH2
O-
O
CH2
C
NH2
O
+H3N CH C
CH2
O-
O
C
NH2
O
asparagine glutamine
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Basic Amino Acids
+H3N CH C
CH2
O-
O
CH2
CH2
CH2
NH3+
+H3N CH C
CH2
O-
O
CH2
CH2
NH
C
NH2
NH2+
lysine arginine
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Benzene-Containing Amino Acids
+H3N CH C
CH2
O-
O
+H3N CH C
CH2
O-
O
OH
phenylalanine tyrosine
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Heterocyclic Amino Acids
+H2N
C O-
O
+H3N CH C
CH2
O-
O
N
NH
+H3N CH C
CH2
O-
O
HN
proline histidine tryptophan
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Configuration of Amino Acids
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Acid–Base Properties of Amino Acids
An amino acid can never exist as an uncharged compound
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Some amino acids have ionizable hydrogens on their side chains
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The isoelectric point (pI) of an amino acid is the pH atwhich it has no net charge
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The pI of an amino acid that has an ionizable side chainis the average of the pKa values of the similarly ionizing groups
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A mixture of amino acids can be separated by electrophoresis on the basis of their pI values
Ninhydrin is used to detect the individual amino acids
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A mixture of amino acids can also be separated on thebasis of polarity
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Ion-exchange chromatography can be used to performpreparative separation of amino acids
Negatively charged resin binds selectively to positivelycharged amino acids
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• Cations bind most strongly to cation-exchange resins
• Anions bind most strongly to anion-exchange resins
• An amino acid analyzer is an instrument that automates ion-exchange chromatography
Ion-Exchange Chromatography
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Resolution of Racemic Mixtures of Amino Acids
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Formation of a Peptide
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Peptide Bond
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Formation of Disulfide Bonds
Disulfides can be reduced to thiols
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The disulfide bridge in proteins contributes to the overallshape of a protein
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Because amino acids have two functional groups, a problem arises when one attempts to make a particular peptide
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Strategy for Making a Specific Peptide Bond
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Amino acids can be added to the growing C-terminal endby repeating these two steps
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When the desired number of amino acids has been added to the chain, the protecting group can be removed
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An Improved Peptide Synthesis Strategy
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The first step in determining the sequence of amino acidsin a peptide or protein is to cleave the disulfide bridges
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The next step is to determine the number and kinds of amino acids in the peptide or protein
protein amino acids6 N HCl
100°C24 h
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The N-terminal amino acid of a peptide or a protein canalso be determined by Edman degradation
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The particular PTH-amino acid can be identified by chromatography using known standards
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The C-terminal amino acid can be identified by treating the protein with carboxypeptidase
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Cyanogen bromide causes the hydrolysis of the amidebond on the C-side of a methionine residue
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Secondary Structure of Proteins
Describe the conformation of segments of the backbonechain of a peptide or protein
Three factors determine the choice of secondarystructure:
• the regional planarity about each peptide bond
• maximization of the number of peptide groups that engage in hydrogen bonding
• adequate separation between nearby R groups
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The -Helix Is Stabilized by Hydrogen Bonds
Prolines are helix breakers
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Two Types of -Pleated Sheets
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Most globular proteins have coil conformations
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The tertiary structure is the three-dimensional arrangement of all the atoms in the protein
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The stabilizing interactions include covalent bonds, hydrogen bonds, electrostatic attractions, and hydrophobic interactions
The tertiary structure is defined by the primary structure
Disulfide bonds are the only covalent bonds that can form when a protein folds
Proteins that have more than one peptide chain arecalled oligomers