ENZYMES
A protein with catalytic properties due to its
power of specific activation
Chemical reactions
Chemical reactions need an initial input of energy =
THE ACTIVATION ENERGY
During this part of the reaction the molecules are
said to be in a transition state.
Reaction pathway
Main! reactions !o "aster
Increasing the temperature make molecules move
faster
Biological systems are very sensitive to temperature
changes.
Enzymes can increase the rate of reactions without
increasing the temperature.
hey do this by lowering the activation energy.
hey create a new reaction pathway !a short cut"
An en#yme controlle$ pathway
Enzyme controlled reactions proceed #$% to #$## times faster
than corresponding non&enzymic reactions.
En#yme str%ct%re
Enzymes are
proteins
hey have a
!lo&%lar shape
' comple( '()
structure
H%man pancreatic amylase
The acti*e site
)ne part of an enzyme*
the active site* is
particularly important
he shape and the
chemical en*ironment
inside the active site
permits a chemical
reaction to proceed
more easily
Co"actors
'n additional non&
protein molecule that is
needed by some
enzymes to help the
reaction
ightly bound cofactors
are called prosthetic
groups
Cofactors that are bound
and released easily are
called coenzymes
+any vitamins are
coenzymes
Nitrogenase enzyme with Fe, Mo and ADP cofactors
The s%&strate
he substrate of an enzyme are the reactants
that are activated by the enzyme
Enzymes are speci"ic to their substrates
he specificity is determined by the acti*e
site
The +oc an$ ,ey Hypothesis
,it between the substrate and the active site of the enzyme is
e(act
-ike a key fits into a lock very precisely
he key is analogous to the enzyme and the substrate
analogous to the lock.
emporary structure called the enzyme&substrate comple(
formed
.roducts have a different shape from the substrate
)nce formed* they are released from the active site
-eaving it free to become attached to another substrate
The +oc an$ ,ey Hypothesis
Enzyme may
be used again
Enzyme-
substrate
complex
E
S
P
E
E
P
Reaction coordinate
The +oc an$ ,ey Hypothesis
his e(plains enzyme specificity
his e(plains the loss of activity when
enzymes denature
The In$%ce$ -it Hypothesis
/ome proteins can change their shape
0conformation1
2hen a substrate combines with an enzyme* it
induces a change in the enzyme3s conformation
he active site is then moulded into a precise
conformation
+aking the chemical environment suitable for the
reaction
he bonds of the substrate are stretched to make the
reaction easier 0lowers activation energy1
The In$%ce$ -it Hypothesis
his e(plains the enzymes that can react with a
range of substrates of similar types
4e(okinase 0a1 without 0b1 with glucose substrate
http566www.biochem.arizona.edu6classes6bioc7896789a6:)E/6E:;<+E/6enzyme=mechanism.html
-actors a""ectin! En#ymes
substrate concentration
p4
temperature
inhibitors
S%&strate concentration. Non(en#ymic reactions
he increase in velocity is proportional to the
substrate concentration
Reaction
velocity
Substrate concentration
S%&strate concentration. En#ymic reactions
,aster reaction but it reaches a saturation point when all the
enzyme molecules are occupied.
If you alter the concentration of the en#yme then V
ma/
will
change too.
Reaction
velocity
Substrate concentration
V
max
The e""ect o" pH
Optimum pH values
Enzyme
activity
Trypsin
Pepsin
pH
1
!
" # 11
The e""ect o" pH
E(treme p4 levels will produce $enat%ration
he structure of the enzyme is changed
he active site is distorted and the substrate
molecules will no longer fit in it
't p4 values slightly different from the enzyme3s
optimum value* small changes in the charges of the
enzyme and it3s substrate molecules will occur
his change in ionisation will affect the binding of
the substrate with the active site.
The e""ect o" temperat%re
>#$ 0the temperat%re coe""icient1 = the increase in
reaction rate with a #$?C rise in temperature.
,or chemical reactions the >#$ = 9 to @
0the rate of the reaction doubles or triples with every
#$?C rise in temperature1
Enzyme&controlled reactions follow this rule as they
are chemical reactions
BA at high temperatures proteins $enat%re
he optimum temperature for an enzyme controlled
reaction will be a balance between the >#$ and
denaturation.
The e""ect o" temperat%re
Temperature $ %&
Enzyme
activity
'
1'
(' ' )' !'
*1'
+enaturation
The e""ect o" temperat%re
,or most enzymes the optimum temperature is about
@$?C
+any are a lot lower*
cold water fish will die at @$?C because their
enzymes denature
' few bacteria have enzymes that can withstand very
high temperatures up to #$$?C
+ost enzymes however are fully denatured at B$?C
Inhi&itors
Inhibitors are chemicals that reduce the rate of
enzymic reactions.
he are usually specific and they work at low
concentrations.
hey block the enzyme but they do not
usually destroy it.
+any drugs and poisons are inhibitors of
enzymes in the nervous system.
The e""ect o" en#yme inhi&ition
Irre*ersi&le inhi&itors. Combine with the
functional groups of the amino acids in the
active site* irreversibly.
E/amples. nerve gases and pesticides*
containing organophosphorus* combine with
serine residues in the enzyme acetylcholine
esterase.
The e""ect o" en#yme inhi&ition
Re*ersi&le inhi&itors. hese can be washed
out of the solution of enzyme by dialysis.
here are two categories.
The e""ect o" en#yme inhi&ition
01 Competiti*e. hese
compete with the
substrate molecules for
the active site.
he inhibitor3s action is
proportional to its
concentration.
Cesembles the substrate3s
structure closely.
Enzyme inhibitor
comple
!eversible
reaction
E " #
E#
The e""ect o" en#yme inhi&ition
S%ccinate -%marate 2 3H
2
2 3e
(
Succinate dehydrogenase
CH
3
COOH
CH
3
COOH CHCOOH
CHCOOH
COOH
COOH
CH
3
,alonate
The e""ect o" en#yme inhi&ition
31 Non(competiti*e. hese are not influenced by the
concentration of the substrate. It inhibits by binding
irreversibly to the enzyme but not at the acti*e site1
E/amples
Cyanide combines with the Iron in the enzymes
cytochrome o(idase.
4eavy metals* A! or H!* combine with 4SH groups.
hese can be removed by using a chelating agent such
as ED'.
Applications o" inhi&itors
Ne!ati*e "ee$&ac5 end point or end product
inhibition
5oisons snake bite* plant alkaloids and nerve
gases.
Me$icine antibiotics* sulphonamides*
sedatives and stimulants
