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Chapter 3
Reaction Mechanism in
Chain Reaction
and
Biological Reactions
Part 2
Kinetics of Biological Reactions
By: Cik Siti Khatijah Jamaludin, FKK UiTM Shah Alam
Enzyme-Substrate Complex
Michealis-Menten Kinetics
Inhibition
of
Enzyme
Reactions
Competitive Inhibition
Uncompetitive Inhibition
Non-competitive Inhibition
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ES
Fast
Examples of enzymes
http://www.google.com/patents/EP1706130A2?cl=en
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Enzyme Kinetics
(Michaelis-Menten Kinetics)
Kinetics is the study of the rated of chemical reactions.
The rates of biological reactions are greatly increased by
enzyme catalysts.
Enzyme kinetics is based upon the elementary kinetics.
The mechanism of enzymes reactions are similar as
catalytic reactions. Substrate (S) adsorb reversibly on the
Enzyme (E), and then reacts to form product (P) and leaves
a free enzyme site for further reaction.
The rate of reaction catalyzed by enzyme can usually be
described by the Michaelis-Menten kinetics.
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Enzyme Kinetics
(Michaelis-Menten Kinetics) cont.
To further illustrate enzyme kinetics, we will use the
example of urea (NH2CONH2) decomposition by the enzyme
urease:
NH2CONH2 + Urease H2O 2NH3 + CO2 + Urease
H2O
S
+
E
P
+
E
The corresponding mechanism is:
k1
r1 = k1(E)(S)
E+S
ES
r2 = k2(ES)
ES k2
E+S
r3 = k3(ES)(W)
ES + W k3
P+E
Activity: write the net rate disappearance of S.
Enzyme Kinetics
(Michaelis-Menten Kinetics) cont.
From previous slide, we see that the net rate disappearance of S is:
-rs = -d(S)/dt = k1(E)(S) k2 (ES)
However, (ES) is immeasurable. Why??
[E S ] =
k 1 [E ][S ]
k 2 + k 3 [W ]
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Enzyme Kinetics
(Michaelis-Menten Kinetics) cont.
However, after we substitute (ES) found in Eq. 7-21 into
Eq. 7-19, Eq. 7-19 still cannot be used.
By substituting Eqs. 7-21 and 7-23 into Eq. 7-19, finally the
measurable net rate of disappearance of S is:
-rS =
k 1k 3[ W][S][Et ]
k 1[S] + k 2 + k 3 [ W ]
Enzyme Kinetics
(Michaelis-Menten Kinetics) cont.
k 1k 3 [ W][S][Et ]
-rS =
k 1[S] + k 2 + k 3 [ W ]
k cat = k 3 [ W ]
k
+ k2
K M = cat
k1
Vmax = k cat [Et ]
(Michaelis-Menten equation)
Eq. 7-25 & Eq. 7-26 Fogler
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-rS =
if,
if,
-rs or rp
K
1
1
1
= M
+
r s Vmax [S ] Vmax
Lineweaver-Burk plot
www.vwmin.org
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Reversible inhibition
Competitive
Inhibition
3 types of
reversible inhibition
Noncompetitive
Inhibition
Uncompetitive
Inhibition
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Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006 Pearson Education, Inc.
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Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006 Pearson Education, Inc.
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Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006 Pearson Education, Inc.
Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006 Pearson Education, Inc.
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Bioreactors
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What is a bioreactor?
Bioreactor: device, usually a vessel, used to direct the activity of a
biological catalyst to achieve a desired chemical transformation.
Fermenter: a type of bioreactor
in which the biocatalyst is a
living cell.
Pre-filtration
Input
Nutrients tank
Waste
Recycle
Product
Bioreactor
Product
separation & purification
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r=
dC s
r C
= max S
dt
K m + CS
Batch operation
with stirring
K m ln
Change of Cs
with time, t
Cs0
+ (C s 0 C s ) = rmax t
Cs
F, Cs0
F, Cs
t=0
V
F
Residence
time
Continuous operation
without stirring
K m ln
Cs0
+ (C s 0 C s ) = rmax t
Cs
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F, Cs0
F, Cs
V
Continuous
operation with
stirring
F, Cs0
FC s 0 FC s rsV = V
Steady state:
dC s
dt
dC s
=0
dt
Michaelisrmax C S
Menten rate: r = K + C
m
S
FC s 0 FC s V
rmax C s
=0
K m + Cs
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F, Cs0
FC s 0 FC s + V
F, Cs
rmax C s
=0
K m + Cs
F
rmax C s
=
V (C s 0 C s ) K m + C s
Cs = K m +
rmax C s
Cs0 Cs
F 1
=
V
A + ns S n A A + n P P
Abiological species i.e organism or cells
Ssubstrate or food supply
Pmetabolic product
nA>1
nA=1
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Kinetics of Reproduction
A + S 2A + P
r = kCACS
r = kCACSO
In batch reactor, dC
A
dt
= kC ACSO
C A = C Ao e kC so t
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Metabolism
A is not reproducing, therefore nA=1
A+ S A+ P
r = kCACS
S P
CA is constant, CA = CAO
In batch reactor,
dCS
= kC AoCS
dt
C S = C So e
CSO C S = C P
kC
Ao t
Material balance
C P = C So (1 e kC Ao t )
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References
Schmidt, L.D. (2005). The Engineering of Chemical Reactions,
2nd edition, New York: Oxford University Press.
Fogler, H.S. (2006). Elements of Chemical Reaction
Engineering, 4th Edition, New Jersey: Prentice Hall.
Levenspiel, O. (1999). Chemical Reaction Engineering, 3rd
Edition, New York: John Wiley.
Pn. Hasyimi Rahmat, FKK UiTM Shah Alam.
Pn. Sharmeela Matali, FKK UiTM Shah Alam.
Pn. Shafiza Hashib, FKK UiTM Shah Alam.
Pn. Siti Wahidah Puasa, FKK UiTM Shah Alam.
CPE624/CHE625
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