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 Chapter 2

Mathematical Modeling and Simulation of Nonlinear

Process in Enzyme Kinetics

Lakshmanan Rajendran, Mohan Chitra Devi,

Carlos Fernandez and Qiuming Peng

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.70914

Abstract
A deep and analytical understanding of the enzyme kinetics has attracted a great attention
of scientists from biology, medicine, chemistry, and pharmacy. Mathematical models of
enzyme kinetics offer several advances for this deep and analytical understanding due to
their in compensable potential in predicting kinetic processes and anticipating appropriate
interventions when required. This chapter concerns mathematical modeling analysis and
simulation of enzyme kinetics. Experimental data and available knowledge on enzyme
mechanics are used in constituting a mathematical model. The models are either in the
form of linear or nonlinear ordinary differential equations or partial differential equations.
These equations are composed of kinetic parameters such as kinetic rate constants, initial
rates, and concentrations of enzymes. The nonlinear nature of enzymatic reactions and a
large number of parameters have caused major issues with regard to efficient simulation
of those reactions. In this work, an enzymatic system that includes Michaelis-Menten and
Ping Pong kinetics is modeled in the form of differential equations. These equations are
solved numerically in which the system parameters are estimated. The numerical results
are compared with the results from an existing work in literature.

Keywords: mathematical modeling, enzyme kinetics, chemical kinetics, nonlinear

reaction-diffusion equation, amperometric, cyclic voltammetry, chronoamperometric

1. Introduction

Enzyme kinetics is a challenging research field nowadays incorporating modern applied mathe-
matics into biotechnology, engineering science, and pharmacy. Moreover, in medical studies,
scientists work on human metabolism to improve the capabilities of some metabolites or enzymes
in metabolic pathways. In industrial applications, kinetics methods are also widely used to

© 2018 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
22 Advanced Chemical Kinetics

develop certain methods for improving functionality of some molecules in a cell. Many problems
in theoretical and experimental biology/chemistry involve the solution of the steady-state reaction
diffusion equation with nonlinear chemical kinetics. Such problems also arise in the formulation
of substrate and product material balances for enzymes immobilized within particles [1, 2], in the
description of substrate transport into microbial cells [3–5], in membrane transport, in the transfer
of oxygen to respiring tissue [6, 7], and in the analysis of any artificial kidney system [8].
To impose the functionality of some molecules in a cell, a mathematical model of such meta-
bolic systems must be constructed and simulated. Most of the dynamical systems can be
approximated by various types of differential and integral equations involving finite number
of variables and parameters. Thus, the future behavior of the system can be predicted if model
kinetics parameters and initial states of the variables are available. In particular, ordinary and
partial differential equations (ODEs and PDEs) are popular in modeling of the metabolic
pathways or enzyme kinetics.

Releasing enzyme-substrate reactions under single-molecule kinetics was reported by Shlomi

et al. [9]. An integral equation method with Michaelis-Menten kinetics to solve nonlinear diffu-
sion problems in spherical coordinates was stated by Tosaka and Miyale [10]. Maalmi et al. [11]
reported numerical and semianalytical solutions of nonlinear equations, which covered diffusiv-
ity, size, bulk concentration of reactant, binding constant of Michaelis-Menten kinetics, and site
reactivity values. Merchant [12] stated the M-M decay reaction terms and the Gray-Scott scheme
along with the semianalytical method to nonlinear reaction-diffusion systems. Indira and
Rajendran [13] described a homotopy perturbation method to obtain substrate and product
concentrations within the enzymatic layers. Removal of substrate from Michaelis-Menten kinetics
governed the extravascular partition in which the analytical solution for the steady-state condi-
tion was investigated by Bucolo and Tripathi [14]. Dang Do and Greenfield [15] utilized the finite
integral transform method to elucidate the problem based on the nonlinear reaction diffusion
coupled with the chemical kinetics of a general shape solid. Chapwanya et al. [16] conveyed an
epidemiological model with the Michaelis-Menten contact rate formulation to investigate varia-
tions in the enzyme kinetics with a simple susceptible infected recovered (SIR) model. Napper
[17] proposed the Michaelis-Menten kinetics model to investigate the oxygen transport to heart
tissue. Regalbuto et al. [18] presented an analytical methodology for obtaining solutions based on
the maximum principle to nonlinear reaction-diffusion boundary value problems.

Rajendran and Saravanakumar [19] discussed mediated bioelectrocatalysis in order to build

bioreactors, bio fuel cells, and biosensors.
Due to the difficulties in solving nonlinear differential equations in enzyme kinetics, some
recent advanced analytical and numerical simulation techniques are used to solve the prob-
lems in chemical kinetics. Thus, in this review, all analytical and numerical works in enzyme
kinetics are summarized.

2. Reaction diffusion systems

Reaction diffusion system is a mathematical model based on how the concentration of sub-
stances/products is disseminated over space changes under the influence of diffusion and a local
 Mathematical Modeling and Simulation of Nonlinear Process in Enzyme Kinetics 23
http://dx.doi.org/10.5772/intechopen.70914

chemical reaction. The substances are transformed into each other in local chemical reaction,
whereas the substances are spread out over a surface in space in diffusion. Reaction-diffusion
(RD) systems arise in many branches of physics, chemistry, biology, ecology, etc. Reviews of the
theory and applications of reaction-diffusion systems can be found in books and numerous
articles (see, for example [20–23]). These arise in a large variety of application areas, such as flow
in porous media [24], heat conduction in plasma [25], combustion problems [26], liquid evapo-
ration [27], and of more recent interest, image processing [28]. A great effort is being made in the
development of the mathematical theory of nonlinear diffusion equations and to obtain exact
solutions for special cases. Their significance not only relies on the huge number of their appli-
cations but also on the fact that they provide with a rather general class of linear and nonlinear
differential operators. In mathematical analysis, it has shown to be a milestone for the develop-
ment of applied, abstract, and numerical analysis as well as for algebra, geometry, and topology.

3. Nonlinear phenomena

The modern theory of the nonlinear reaction diffusion process is an important field in today’s
science. The nonlinear system and coherent structures represent an interdisciplinary area with
many nonlinear applications in various fields. Those applications can be divided into six disci-
plines: chemistry (autocatalytic chemical and enzyme reactions), physics (nonlinear optics and
electric circuits, plasmas and states of solid, condensed atomic gases, hydrodynamics, galaxy
dynamics and cosmology, fluid dynamics, and celestial mechanics), general relativity, biology
(biofuel cell, bioreactor and biosensor, atmosphere and oceans, and animal dispersal), random
media, and modern telecommunications. A great variety of phenomena in physics, chemistry, or
biology can be described by nonlinear ODE/PDEs and particularly by reaction-diffusion equa-
tions. For these reasons, the theory of the analytical solutions of the reaction-diffusion equations
is considered.

In reaction diffusion systems, nonlinear phenomena play a crucial role in applied mathematics
and chemistry. Exact (closed-form) solution of nonlinear reaction diffusion equations plays an
important role in the proper understanding of qualitative features of many phenomena and
processes in various areas of natural science. The main result obtained from reaction and
diffusion systems is that nonlinear phenomena include diversity of stationary and spatio-
temporary dissipative patterns, oscillations, different types of waves, excitability, biostability,
etc. But it is difficult for us to obtain the exact solution for these problems. The investigation of
exact solution of nonlinear equation is interesting and important. In general, this results in the
need to solve linear and nonlinear reaction diffusion equations with complex boundary condi-
tions. The enzyme kinetics in biochemical systems have usually been modeled by differential
equations, which are based only on reaction without spatial dependence of the various con-
centrations. The dimensionless nonlinear reaction diffusion equations are described below:

∂S
¼ ∇2 S f ðR; τ; S; PÞ (1)
∂τ
∂P
¼ ∇2 P þ gðR; τ; S; PÞ (2)
∂τ
24 Advanced Chemical Kinetics

where S and P represent the dimensionless concentrations of substrate and product, τ repre-
sents the dimensionless time, and R is the dimensionless radial co-ordinate of the particle. The
first term on the right-hand side of the above equation accounts for active species (substrate or
product) diffusion, whereas the second term f(R, τ, S, P) and g(R, τ, S, P) represents the homo-
geneous reaction term (nonlinear term), generally polynomial in the concentrations and time.

4. Common geometries and nonlinear reaction

Most commonly used electrodes/microelectrodes consist of a conducting metal/glassy carbon

or semiconducting surface embedded in an insulating wall. When the conducting surface is a
rectangle or disc of a few millimeters, this is known as a “planar” electrode. Diffusion to this
surface is effectively planar (the effects of the edges are negligible), hence the nonlinear one-
dimensional reaction diffusion equation is given by:

∂½CŠ ∂2 ½CŠ
¼D þ f ð½CŠÞ (3)
∂t ∂x2

Two other electrode geometries where diffusion occurs in only one spatial dimension are the
hemispherical and hemicylindrical electrodes. The nonlinear two-dimensional (hemispherical
or spherical) reaction diffusion equation is:
 2 
∂½CŠ ∂ ½CŠ 2 ∂½CŠ
¼D þ þ f ð½CŠÞ (4)
∂t ∂x2 r ∂r

and for the latter is:

 2 
∂½CŠ ∂ ½CŠ 1 ∂½CŠ
¼D þ þ f ð½CŠÞ (5)
∂t ∂x2 r ∂r

The hemisphere can be achieved experimentally via a small drop of mercury positioned over a
smaller conducting disc. A soft polymer, rubber, or other similar materials are usually
employed to fabricate a hemicylinder. The electrodes are usually employed in theoretical
studies due to the low dimensionality of the mass-transport equation. Additional terms such
as diffusion and nonlinear reaction allow the equation to be solved analytically. Furthermore,
the electrodes are not accurately or easily fabricated for practical geometries.

The corresponding nonlinear reaction-diffusion issues in enzyme kinetics are focused on the
mathematical resolution. Table 1 shows the response of particular electrodes with special
emphasis on earlier theoretical works in the field.

Example 1: Michaelis-Menten kinetics and microcylinder electrodes

The model is written for an enzyme reaction to generate an electro-active product (e.g.,
hydrogen peroxide from an oxidase enzyme) that reacts at an immobilization matrix, which
Author Reference Experimental Enzymatic scheme Modeling method
technique

Analytical solutions
0
G. Rahamathunissa Journal of theoretical and Computational Amperometric KM
h 0i k
c 0 kE Danckwort’s expression
et al. Chemistry, 7(1)(2008)113–138 S þ C!½SCŠ ! PC !P þ C C !C

R. Senthamarai et al. Electrochemical Acta 53(2008)3566–3578 Chronoamperometric A + e!B Analytical

k
B þ Z!A þ product

G. Rahamathunissa Journal Mathematical Chemistry 44(2008)849– Amperometric KM

E þ S$ES !E þ P
K2 Variation iteration method
L. Rajendran 801 (VIM)
A. Meena et al. Journal Mathematical Chemistry, 48(2010)179– Amperometric K1
E þ S! ES ! E þ P He’s variation iteration

Mathematical Modeling and Simulation of Nonlinear Process in Enzyme Kinetics

186 K 1 method
A. Eswari, L. Rajendran Journal of Electroanalytical Chemistry 641(2010) Amperometric K1
S þ E1 $½E1 SŠ! P þ E2
Kcat Homotopy perturbation
35–44 K2 method (HPM)
P. Manimozhi et al. Sensors and Actuators B 147(2010)290–297 Amperometric k1
E þ S!ES!E þ P
kc Variational iteration and
k 1 homotopy perturbation
ES + S$ES3 method (VIM & HPM)
S. Logambal, L. Electrochemical Acta 55(2010)5230–5238 Amperometric KA Homotopy perturbation
A þ E2 !B þ E1
Rajendran KE method (HPM)
E1 þ S!E2 þ P
A. Meena, L. Rajendran Journal of Electroanalytical Chemistry, 6411 Amperometric and E + S$[ES]!E + P Homotopy perturbation

http://dx.doi.org/10.5772/intechopen.70914
(2010)50–59 Potentiometric method (HPM)
S. Anitha, L. Rajendran Journal of Physical Chemistry 114(2010)7030– Amperometric DE K Reduction of order
B!B þ S!A þ Z ! A ! B
7037 method
P. Manimozhi, L. Journal of Electroanalytical Chemistry 647(2010) Amperometric Ka Analytical
S þ E$ES
Rajendran 87–92 Kα
K cat 0
ES ! S þ E
A. Eswari, L. Rajendran Journal of Electroanalytical Chemistry 648(2010) Amperometric K1
S þ E1 $ ½E1 SŠ ! P þ E2 Homotopy perturbation
36–46 K 1 method (HPM)
A. Eswari, L. Rajendran Russian Journal of Electroanalytical Chemistry Cyclic voltammetry EA þ e $ B Laplace Transformation
47(2011)195–204 k1
C B! Products
A. Eswari, L. Rajendran Russian Journal of Electroanalytical Chemistry Cyclic voltammetry EA þ e $ B Homotopy perturbation
47(2011)205–212 C2 B þ B! Products
k1 method (HPM)

25
 26
Advanced Chemical Kinetics
Author Reference Experimental Enzymatic scheme Modeling method
technique

A. Eswari, L. Rajendran Journal of Electroanalytical Chemistry 651(2011) Chronoamperometric O þ ne $ R Homotopy perturbation

173–184 k
R þ Z!O þ Products method (HPM)

G. Rahamathunissa Journal of Mathematical Chemistry 9(2011)457– Chronoamperometric kM

S þ E$ E S!E þ P
k2 VIM
et al. 474
S. Logambal, L. Journal of Membrane Sciences 373(2011)20–28 Amperometric k
EOX þ S$ E S!Ered þ P
1 k2 Homotopy perturbation
Rajendran kM method (HPM)
k3
Ered þ O2 ! EOX þ H2 O2
S. Anitha et al. Electrochimica Acta 56(2011)3345–3352 Amperometric KM kcat Homotopy perturbation
S þ E1 $ ½E1 SŠ!P þ E2 A ! B
method (HPM)
K. Indra, L. Rajendran Electrochimica Acta 56(2011)6411–6419 Chronoamperometric PPO
S1 þ O2 ! P2 þ H 2 O V 1 Homotopy perturbation
method (HPM)
þ k0
P2 þ 2e þ 2H $S2 E0
kr
1 PPO
S2 þ O2 ! P2 þ H 2 O V 2
2
S. Thiagarajan et al. Journal of Mathematical Chemistry DOI: Chronoamperometric kM kcat Homotopy perturbation
S þ Mox $ S Mox !P þ Mred
10.1007/s10919-011-9854-z method (HPM)
M. Uma Maheswari, L. Journal of Mathematical Chemistry DOI: Chronoamperometric K1
E þ S $ k 1 ES!E þ P
k2 Homotopy perturbation
Rajendran 10.1007/s10919-011-9853-0 method (HPM)
P. Rijiravanich et al. Electroanalytical Chemistry 589(2006)249 Amperometric O2 þ 2catechol ! 2o quinone þ 2 H 2 O Theory and experiment
o quinone þ 2 Hþ þ 2e ! catechol

A. Eswari, L. Rajendran Journal of Electroanalytical Chemistry 660(2011) Amperometric O2 þ 2catechol ! 2o quinone þ 2 H 2 O VIM
200–208 o quinone þ 2 Hþ þ 2e ! catechol

G. Varatharajan, L. Applied Mathematics 2(2011)1140–1147 Amperometric K1 kcat Homotopy perturbation

S þ E $ C!P þ E
Rajendran k 1 method (HPM)
k3
E!Ei
K. Venugopal et al. Journal of Biomedical Science and Engineering 4 Chronoamperometric O2 þ 2catechol ! 2o quinone þ 2 H 2 O Homotopy perturbation
(2011)631–641 o quinone þ 2 Hþ þ 2e ! catechol method (HPM)

K. Indra, L. Rajendran Journal of Mathematical Chemistry DOI: Chronoamperometric A$BþC Homotopy perturbation
10.1007/s10910-011-9968-3 B  e ! products method (HPM)

V. Margret Ponrani, L. Journal of Mathematical Chemistry DOI: Amperometric k

G þ E$X!F þ E
1 k 2 Homotopy perturbation
Rajendran 10.1007/s10910-011-9973-6 K1 k2 method (HPM)
Author Reference Experimental Enzymatic scheme Modeling method
technique

S. Sevukaperumal et al. Applied Mathematics 3(2012)373–381 Chronoamperometric Glucose þ O2 gluconicacid þ H 2 O2 Homotopy analysis
Glucoseoxidase
!
method (HPM)
Catalase 1
H 2 O2 ! H 2 O2 þ O2
2
Numerical solution
R. Baronas et al. Biosensors and Bioelectronics 19(2004)915–922 Amperometric S ! P!S
E Finite-difference technique

R. Baronas Electrochimica Acta 240(2017)399–407 Amperometric S þ E $kk1 1 ES ! P þ E Numerical simulation and

biosensor E analytical solution
S!P

Mathematical Modeling and Simulation of Nonlinear Process in Enzyme Kinetics

V. Ašerisa et al. Journal of Electroanalytical Chemistry 685(2012) Amperometricparallel E1 1 Digital simulation-finite-
S1 ! P 1
63–71 substrates conversion 2 difference technique
E2
S1 þ S2 !P2
V. Flexer et al. Bioelectrochemistry 74(2008)201–209 Cyclic voltammetry kcat Numerical simulation
S þ EOX $kk1 1 ES!P þ Ered

R. Baronas et al. Chemometrics and Intelligent Laboratory Amperometric k 2i Numerical

E þ Si k1i $ ESi !E þ Pi , i ¼ 1, …, k
Systems 126(2013)108–116
R. Baronas Nonlinear Analysis: Modeling and Control 9(3) Amperometric E
S!P Digital simulation-finite-
(2004)203–218 difference technique.
R. Baronas et al. Sensors 12(2012)9146–9160 Amperometric k1 Finite-difference

http://dx.doi.org/10.5772/intechopen.70914
EOX þ S! Ered þ P
k2
Ered !EOX þ ne e

R. Baronas et al. J. Mathematical Chemistry 32 (2)(2002)225–237 Amperometric E

S!P Numerical simulation

R. Baronas et al. Mathematical Modeling of Biosensors, Springer Amperometric All enzyme reactions Analytical and numerical
Series on chemical sensors and biosensors (2009) methods
L. Rajendran Biosensor: Modeling and Simulation of Amperometric All enzyme reactions Analytical, HPM&HAM,
Diffusion-Limited Process, Chemical Sensors: VIM,ADM, etc.
Simulation and Modeling,
GhenadiiKorotcenkov (Ed.), Electrochemical
Sensors, Vol. 5, Momentum Press, LLC, New
York (2013)

Table 1. Contributions to the theoretical modeling of enzymatic electrodes.

27
28 Advanced Chemical Kinetics

is metallically conducting sites/particles. The reaction within the film under the Michaelis-
Menten kinetics may be written as follows:
k1 kcat
S þ E1 ⇔ ½E1 SŠ!P þ E2 (6)
k 1

The consumption rate of S is given by k1cScE k 1cES, where ci denotes the concentration of
species i. The rate is equivalent to (kcat/KM) cScE, where KM is the Michaelis constant, defined as
KM = (k 1 + kcat)/k1. The consumption rate of S in the film is compensated by diffusion. If the
solution is stirred uniformly, so that S is constantly supplied to the film, the mass balance for S
can be written in cylindrical coordinates:


DS d dcS kcat cE cS
r ¼0 (7)
r dr dr cS þ KM

where cS is the concentration profile of substrate, cE is the concentration profile of enzyme, DS

is its diffusion coefficient, and KM is the Michaelis constant. The rate of consumption will be
v(r) = k cH, where k is the rate constant for the hydrogen peroxide reaction and cH is the
peroxide concentration. Then, the equation of continuum for hydrogen peroxide is generally
expressed in the steady-state by


DH d dcH kcat cE cS
r þ vðrÞ ¼ 0 (8)
r dr dr cS þ K M

At the electrode surface (r0) and at the film surface (r1), the boundary conditions are [29]:

dcS
r ¼ r0 : ¼ 0, cH ¼ 0
dr (9)
r ¼ r1 : cS ¼ c∗S , cH ¼ 0

where c∗S is the bulk concentration of S scaled by the partition coefficient of the film. The
current is provided by the consumption rate at each site. Thus, the total current at an electrode
of length L is expressed by [29]
ðr1
I=nF ¼ 2πL rv dr (10)
r0

The analytical results of the problem are discussed by Eswari and Rajendran [30].

Example 2: enzyme catalysis reaction

The reactions without spatial dependence on various concentrations have modeled the
enzyme kinetics in biochemical systems. Nonlinear systems of ordinary differential equations
are solely based on that. Michaelis and Menten were pioneers in explaining the enzyme
reaction model. In addition, they also reported the free enzyme binding to the reactant, which
 Mathematical Modeling and Simulation of Nonlinear Process in Enzyme Kinetics 29
http://dx.doi.org/10.5772/intechopen.70914

produced an enzyme-reactant complex. Eq. (11) illustrates the Michaelis-Menten kinetics, in

which the enzyme-substrate complex is formed after the enzyme is combined with the sub-
strate.
k1 k2
E þ S $ ES!E þ P (11)
k 1

As can be seen from Eq. (11), the product P is released by the binding of substrate S with enzyme
E. The product released is not reversible; however, the substrate binding is reversible. The
reactants’ concentrations in Eq. (11) are represented by the following letters:

s ¼ ½SŠ, e ¼ ½EŠ, c ¼ ½SEŠ, p ¼ ½PŠ (12)

The law of mass action leads to the system of following nonlinear reaction equations [31],

ds
¼ k1 es þ k 1 c (13a)
dt
de
¼ k1 es þ ðk 1 þ k2 Þc (13b)
dt
dc
¼ k1 es ðk 1 þ k2 Þc (13c)
dt
dp
¼ k2 c (13d)
dt

where k1 is the forward rate of ES complex formation and k 1 is the backward rate constant.
The above problem is discussed theoretically by Meena et al. [32].

Example 3: Michaelis-Menten mechanism for co-substrate and substrate

Figure 1 illustrates Michaelis-Menten reaction kinetics scheme for co-substrate and substrate.
Limoges et al. [33] reported for a redox enzymatic homogenous system along with one-
dimensional mass transport equation a concise discussion and derivation.
When the enzyme is being solubilized, the electrochemical signal that is produced during the
reaction is governed by the following set of nonlinear partial differential equations.

∂½QŠ ∂2 ½QŠ C0E

¼ DP 1 1 1 1
(14)
∂t ∂x2 k1 ½SŠ þ k1, 2 þ k2, 2 þ k2 ½QŠ

∂½SŠ ∂2 ½SŠ C0E

¼ DS 1 1 1 1
(15)
∂t ∂x2 k1 ½SŠ þ k1, 2 þ k2, 2 þ k2 ½QŠ

where DP , DS are the diffusion coefficients of co-substrate and substrate, respectively; Q , S are
the concentrations of co-substrate and substrate, respectively; x is the distance from the
30 Advanced Chemical Kinetics

Figure 1. Reaction scheme for substrate and co-substrate.

electrode surface; C0S is the bulk concentration of substrate; C0E is the total concentration of
enzyme; k1, k2 , 2, and k2 are the reaction rate constants; and t is the time. The initial and
boundary conditions for Eqs. (14) and (15) are given by:

t ¼ 0, x ≥ 0, and x ¼ ∞, x ≥ 0, ½QŠ ¼ 0, ½SŠ ¼ C0S (16)

C0P ∂½SŠ
x ¼ 0, t ≥ 0 : ½QŠ ¼ h  i , ¼0 (17)
1 þ exp F
E E0PQ ∂x
RT

x ¼ ∞, ∂½QŠ=∂x ¼ 0 (18)

The analytical expressions corresponding to the concentration of co-substrate for steady and
nonsteady state conditions have been obtained by solving the above nonlinear equation using
a new approach to homotopy perturbation method (HPM). Analytical expressions of the
plateau current are also presented for steady and nonsteady state conditions:


∂ ½ QŠ
i ¼ FSDP (19)
∂x x¼0

where E is the electrode potential, E0PQ is the standard potential of the P/Q couple, F is the
Faraday constant, and S is the surface area of the electrode. The above problem is discussed
theoretically by Rasi et al. [34].

5. Analytical solutions

To study many of the physical phenomena, the exact solutions of nonlinear partial or ordinary
differential equations play an important role. In order to understand the mechanism of com-
plicated dynamical processes and physical phenomena modeled by nonlinear differential
equations, the existence of approximate analytical and exact solutions is very important. In
 Mathematical Modeling and Simulation of Nonlinear Process in Enzyme Kinetics 31
http://dx.doi.org/10.5772/intechopen.70914

addition, nonlinear differential equations can also assist to investigate the stability of these
solutions as well as checking the simulation analysis. Nonlinear partial differential equations
govern a significant variety of phenomena including physical, chemical, and biological. The
development of techniques aimed at exact solutions of nonlinear differential equations with
nonsteady and steady state [35] has been one of the most exciting advances of nonlinear
science and theoretical physics/chemistry. An important role in nonlinear science is played by
exact solutions of differential equations. Furthermore, this can be especially observed in
nonlinear physical chemistry science. This can be attributed to the provision of physical
information as well as more insight into the physical aspects of the problem, which could lead
to further applications. Over the past few decades, different methods have been reported to
solve analytical solutions such as Tanh-sech [36], extended tanh [37], Jacobi elliptic function
expansion [39], hyperbolic function [38], F-expansion [40], and the First integral [41]. To solve
different types of nonlinear systems of PDEs, the sine-cosine method [42] has been employed.
A variety of powerful analytical methods such as homotopy perturbation method [43–45],
homotopy analysis method [46, 47], Adomian decomposition method [48, 49], wavelet trans-
form method [50], etc. are applied to solve the nonlinear problems (e.g., Eqs. (8) and (13)–(15))
in chemical kinetics [51].

6. Numerical solutions

Many differential equations cannot be solved analytically. For practical purpose, however,
such as in physical engineering sciences, a numerical approximation to the solution is often
sufficient. The numerical method is mainly to solve complex problem physically or geometri-
cally. It is also used to validate the experimental results. Some of the nonlinear equations in
chemical kinetics were solved using numerical methods [52–56].

7. Summary

Most mathematical models of enzyme kinetics are based on reaction diffusion equations or
rate equations containing nonlinear terms related to the kinetics of the enzyme reaction.
Powerful and accurate analytical (HPM, HAM, ADM, etc.) and numerical mathematical
methods have been employed for their resolution under steady and nonsteady state condi-
tions. The theoretical results provide very useful insight into the effects on the performance of
the thickness and structure of the enzymatic film, the loading of the different species, the
diffusivity of the mediator, etc. Also, the theoretical modeling and simulation of these systems
enable us to characterize the enzymatic reactions (i.e., rate constant, turnover rate, and
Michaelis-Menten constants).

In spite of the above-mentioned benefits, there are only limited theoretical studies addressing
kinetics of enzyme reaction and most of them include a number of simplifying assumptions
mainly related to the mass and charge transport inside and outside the biocatalyst film, the
enzymatic kinetic scheme, and the electrode morphology. Experimental validation of proposed
32 Advanced Chemical Kinetics

models is even more seldom. Therefore, more effort in the future research is needed in this
direction in order to develop more detailed models and accurate simulations that can assist the
rational development and optimization of enzyme electrodes.

Author details

Lakshmanan Rajendran1*, Mohan Chitra Devi1, Carlos Fernandez2 and Qiuming Peng3

*Address all correspondence to: [email protected]

1 Department of Mathematics, Sethu Institute of Technology, Pulloor, Kariapatti, India
2 School of Pharmacy and Life Sciences, Robert Gordon University, UK

3 State Key Laboratory of Metastable Materials Science and Technology, Yanshan University,
Qinhuangdao, China

References

[1] Aris R. The Mathematical Theory of Diffusion and Reaction in Permeable Catalysts. Vol.
1. Clarendon: Oxford; 1975
[2] Engasser JM, Horvath C. Effect of internal diffusion in heterogeneous enzyme systems:
Evolution of true kinetic parameters and substrate diffusity. Journal of Theoretical Biol-
ogy. 1973;42:137-155

[3] Cheviollotte P. Relation between the reaction cytochrom oxidase-oxygen and oxygen
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