A Simple Analytical Expression of A Non-Linear Boundary Value Problem For An Immobilized Oxidase Enzyme Electrode Using The New Homotopy Perturbation Method

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Frontiers in Sensors (FS) Volume 2, 2014
A Simple Analytical Expression of a Non-Linear

Boundary Value Problem for an Immobilized
Oxidase Enzyme Electrode Using the New
Homotopy Perturbation Method
V.Ananthaswamy1, C. Chowmiya2, M. Subha3
Department of Mathematics, The Madura College (Autonomous), Maduri, Tamil Nadu, India
M.Phil.,Mathematics, The Madura College (Autonomous), Maduri, Tamil Nadu, India
1
2
3
Department of Mathematics, MSNPM Womens College, Poovanthi, Sivagangai Dt., Tamil Nadu, India
ananthu9777@rediffmail.com*; 2chowmiya24692@gmail.com; 3subhaamsc@rediffmailcom
Abstract
In this article a mathematical model of an immobilized
oxidase enzyme electrode is presented. The model is based
on the three reaction-diffusion equations containing a nonlinear reaction term under the steady state conditions. A
simple analytical expressions pertaining to concentrations of
the immobilization of three enzyme substrates are obtained
by using the new Homotopy perturbation method (HPM). A
simple analytical expression of the concentrations of
substrate, oxygen and oxidized mediator and current was
obtained in terms of the thiele moduli and the small values
of the normalized surface concentration of substrate Bs ,
thenormalized surface concentration of oxygen Bo and the
normalized surface concentration of oxidized mediator Bm .
These analytical solutions are compared with the numerical
simulation. A good agreement between analytical
expressions and numerical results is noted.
Keywords
Enzyme Electrodes; Non-linear Boundary Value Problem;
Reaction-diffusion Equations; Biosensor; New Homotopy
Perturbation Method; Numerical Simulation
Introduction
The basic concepts of enzyme electrodeswereintroduced by Clark and Lyons [Clark et. al (1962), Lyons et.al
(1962)]. Many kinds of biosensors based on
electrochemical enzyme electrodes have been studied
and a majority of this device operates in an
amperometric mode [Scheller et.al (1992), schulbert et.
al (1992)]. Biosensors are usually classified into various
groups either by type of transducer employed
(electrochemical, optical, piezoelectric, and thermal) or
by the kind of bio-recognition element utilized
(antibody, enzymes, nucleic acids, and whole cells).
Both components of the biosensor, namely, the bio
32
recognition element (referred as a receptor) and

transduction platform (referred as a transducer) play
an important role in the construction of a sensitive and
specific device for the analyte of interest.
Schulmeister has described models for multilayerand
multienzyme electrodes; these models assumed
operationof the electrode under diffusion control, such
that the enzymekinetics are linear with substrate
[Schulmeister et. al (1990) and Pfeiffer et. al (1993)].
The kinetics is described by a parabolic differential
equation with linear inhomogeneities. Thefact that
relatively few enzyme electrodes have been
commercialized may be due to the technical
problemsassociated with either the enzyme reaction or
the underlying product/substrate-sensitiveelectrode,
such as the availability of appropriate enzymes, their
successful
immobilization,
andprobably
most
importantly the achievement of an acceptablecatalytic
lifetime of the enzyme.
Leypoldt and Gough have described a model for a two
substrate enzyme electrode with the non-linear
enzyme reaction[Leypoldt et. al (1984) , Gough et.al
(1984)].This model to describe the behaviorof a glucose
oxidase electrode. Bergel and Comtat describe the
transient response of a mediated amperometric
enzyme electrode by using an implicit finite difference
method [Bergal et. al (1984), Comtat et. al (1984)]. A
two-substrate enzyme electrode was described by
Gooding and Hall [Gooding et. al (1996) , Hall et. al
(2012)].The development of models for enzyme
electrodesprovides a better understanding of the
individual processesinfluencing the response of the
device, and this informationmay be used as a guide for
directions for improvement of thesensor design.
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The importance of enzyme electrode and the various

approaches to enzyme electrochemistry has been
discussed. The current response has been also
observed experimentally for mediated enzyme
electrodes employing glucose oxidase [Martens et. al
(1995), Hindle et. al (1995), Hall et. al (1995) and
Pallachi et. al (1990), Turner et.al (1990)].The
membranes provide an ideal support for the
immobilization of the biocatalyst. Substrate partition
at the membrane/fluid inter-phase can be used to
improve the selectivity of the catalytic reaction
towards the desired products [Trevan et. al (1981)].
Homogeneous membranes are used as carries for
immobilization of enzymes [Simon et. al (2002),
Hailweil et. al (2002), Cass et. al (2002)] and also used
in biomaterials, bio-separators and biosensors [Liu
et.al (1996) ,Zhang et. al (1996) , Yu et.al , Deng et. al
(1996) ].
In this paper, we describe a model for thisthreesubstrate enzyme electrode and employ the model
toinvestigate the influence of the oxygen on the
current responseof a mediated oxidase electrode. To
our knowledge, no general analytical expressions that
describe concentration of substrate, oxygen and
oxidized mediator for various of the thiele modulus s2 ,
o2 and m2 and the normalized parameters Bs , Bo and

Bm have been reported. However, in general,
analytical solutions of non-linear differential equations
are more important manipulation and analysis. For
this reason, we have derived that analytical
expressions corresponding to the concentrations of
substrate, oxygen and oxidized mediator in an oxidase
enzyme electrode using new Homotopy perturbation
method. This method is reliable and highly accurate in
handling non-linear problems.
Mathematical Formulation of the Boundary
Value Problem
The details of the model adopted have been fully
described in Martens and Hall [Martens et. al (1994),
Hall et.al (1994)]. Figure.1 represents the general
kinetic reaction scheme of enzyme-membrane
electrode geometry [Gooding et. al (1996), Hall et.al
(1996)].The general reaction scheme for an
immobilized oxidase inthe presence of two oxidants
can be written as follows:
k
k
EOX + S
ES
Ered + P
3
k
Ered + O2 EOX + H 2 O2
We assume that the concentrations of all reactants and

enzyme intermediates remain constant for all time.
Also the concentration of total active enzyme [ Et ] and
the reactants in the bulk electrode remain constant. We
can consider that the diffusion of the reactants can be
described by Ficks second law and the enzymes are
assumed to be uniformly dispersed throughout the
matrix. The enzyme activity is not a function of
position. The reaction/diffusion equations corresponding to the concentrations of substrate, oxygen and
oxidized mediator within a matrixcan be expressed
as[14]
O [ Med ] 1
d 2 [S ]
OX
s
Ds
= k3 [ Et ] 1 + 2 +
+
2
S ]
m
o
dy
[
Dm
d 2 [ MedOX ] [O2 ] / o + [ MedOX ] / m
dy 2
[ MedOX ] / m
[O ] [ Med ] 1
OX
s
= k3 [ Et ] 1 + 2 +
+
S ]
m
o
[
Do
d 2 [O2 ] [O2 ] / o + [ MedOX ] / m
dy 2
[O2 ] / o
[O ] [ Med ] 1
OX
s
= k3 [ Et ] 1 + 2 +
+
S ]
m
o
[
(4)
(5)
(6)
where [ S ] , [ MedOX ] and [O2 ] are the concentrations

of substrate, oxidized mediator and oxygen and y is
distance from the electrode. D s , Dm and Do are the
diffusion coefficients of substrate, oxidized mediator
and oxygen. [ Et ] Denotes the concentration of the
total active enzyme in the matrix and =
s
( k2 + k3 ) / k1 ,
o = k3 / k4 & m = k3 / k5 represent reaction constants

of substrate, oxygen and oxidized mediator
respectively. The boundary conditions are given by
When y = d ,
=
[O2 ]
=
K o [O2 ] ,=
S ]b
[O
[ S ] [=
2 ]b
=
MedOX ]b K m [ MedOX ]
[ MedOX ] [=
K s [ S ]b ,
(7)
when y = 0,
O2 ] / dy
[ MedOX ] = [ MedOX ]b d [=
d=
[ S ] / dy 0
(8)
(1)
Here [ S ]b , [O2 ]b [ MedOX ]b and [ S ] , [O2 ] , [ MedOX ]
(2)
are the bulk concentrations of substrate, oxygen and

oxidized mediator species. K o , K s and K m are the
k4
(3)
k
Ered + MedOX
EOX + Med red
33
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partition coefficients for oxygen, substrate and

oxidized mediator respectively. Equation (4) can be
represented in the normalized form using the
following normalized parameters.
[S ] ;
Fs =
[ S ]b
Bs =
s2 =
[O2 ]
Fo =
[O2 ]b
[ S ]b
s
d 2 k3 [ Et ]
Ds [ S ]b
Bo =
; o2 =
[ MedOX ] ;
Fm =
[ MedOX ] b
[O2 ]b
o
; Bm =
d 2 k3 [ Et ]
Do [O2 ]b
[ MedOX ]b
m
; m2 =
y
x= ;
d
d 2 k3 [ Et ]
Dm [ MedOX ]b
(9)
(10)
(11)
where Fs , Fo and Fm represent the normalized

concentrations of substrate, oxygen and oxidized
mediator and Bs , Bo and Bm are the corresponding
normalized surface concentrations. The surface
concentration is the ratio of the bulk concentration and
the reaction constants. s2 , o2 and m2 denote the
thiele moduli of substrate, oxygen and oxidized
mediator, respectively. Thiele modulus 2 represents
the ratio of the characteristic time of the enzymatic
reaction to that of substrate diffusion and dis the
thickness of the enzyme layer. The systems of three
non-linear reaction/diffusion equations in normalized
form are
d 2 Fs
dx 2
1
=
1
1
1+
+
Fo Bo + Fm Bm Fs Bs
2
s
(12)
d Fo
Fo Bo
1
= o2
2
1
1
F
B
F
B
+
dx
m m 1+
o o
+
F
B
F
B
F
+
o o
m m
s Bs
(13)
1
1
1+
+
F
B
F
B
F
+
o o
m m
s Bs
(14)
d 2 Fm
dx 2
Fm Bm
= m2
Fo Bo + Fm Bm
The boundary conditions become

F=
F=
F=
1 at =
x 1
s
o
m
(15)
dFo dFs
= 0 at=
x 0
Fm = 1 , =
dx
dx
(16)
The normalized current J OX is given by,

dF
J OX = m
dx x = 0
34
(17)
Analytical Expression of the Normalized

Surface Concentrations Using the New
Homotopy Perturbation Method
Linear and non-linear phenomena are of fundamental
importance in various fields of science and
engineering. Most models of real life problems are
still very difficult to solve. Therefore, approximate
analytical solutions such as Homotopy perturbation
method (HPM) [Gohri et. al (2007), Ozis et. al (2007),
Li et. al (2006), Mousa et. al (2008), He (1999 and 2003),
Ariel (2010), Ananthaswamy et. al (2012 and 2013)]
were introduced. This method is the most effective
and convenient ones for both linear and non-linear
equations. Perturbation method is based on assuming
a small parameter. The majority of non-linear
problems, especially those having strong non-linearity,
have no small parameters at all and the approximate
solutions obtained by the perturbation methods, in
most cases, are valid only for small values of the small
parameter. Generally, the perturbation solutions are
uniformly valid as long as a scientific system
parameter is small. However, we cannot rely fully on
the approximations, because there is no criterion on
which the small parameter should exists. Thus, it is
essential to check the validity of the approximations
numerically and/or experimentally. To overcome these
difficulties, HPM have been proposed recently.
Recently, many authors have applied the Homotopy
perturbation method (HPM) to solve the non-linear
boundary value problem in physics and engineering
sciences [Ghori et. al (2007), Ozis et. al (2007), Mousa
et. al (2008)]. Recently this method is also used to solve
some of the non-linear problem in physical sciences
[He 1999 and 2003 ]. This method is a combination of
Homotopy in topology and classic perturbation
techniques. Ji-Huan He used to solve the Lighthill
equation [Mousa et. al (2008)], the Diffusion equation
[He 1999] and the Blasius equation [He 2003]. The
HPM is unique in its applicability, accuracy and
efficiency. The HPM uses the imbedding parameter p
as a small parameter, and only a few iterations are
needed to search for an asymptotic solution. The
simple analytical expressions of the concentrations of
substrate, oxygen and oxidized mediator are as
follows:
(18)
(19)
Fs (=
x)
k12 2
x 1 +1
2
Fo (=
x)
k22 2
x 1 +1
2
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k32 2
x x +1
2
Fm (=
x)
where,
(20)
increases, the corresponding normalized concentration

of substrate Fs , oxygen Fo and mediator Fm decreases
for some fixed values of Bo , Bm when 2s = 1, o2 = 1
and m2 = 1 .
( Bo + Bm ) Bs
k12 = s2
( Bo + Bm ) Bs + Bs + ( Bo + Bm )
(21)
Bo Bs
k22 = o2
( Bo + Bm ) Bs + Bs + ( Bo + Bm )
(22)
Bm Bs
k32 = m2
( Bo + Bm ) Bs + Bs + ( Bo + Bm )
(23)
increases, the corresponding normalized concentrations

of substrate Fs , oxygen Fo decreases for some fixed
The corresponding normalized current using eqn. (20):
values of Bs , Bm when 2s = 1, o2 = 1 . Figure. 4 (c) it is
J OX =
k32
2
(24)
where k32 is defined by the eqn. (23).
The non-linear reaction-diffusion equations eqns. (12)(14) for the boundary conditions eqns. (15) and (16) are
also solved numerically. We have used the function
pdex4 in Scilab/Matlab numerical software to solve
numerically, the initial-boundary value problems for
parabolic-elliptic partial differential equations. This
numerical solution is compared with our simple
analytical equations in Figs. (2) - (6). A satisfactory
agreement is noted for various values of the thiele
moduli s2 , o2 and m2 and possible small values of
the dimensionless parameters Bs , Bo and Bm .
Figure.1 is the schematic model of an enzymemembrane electrode. Figure2 is the normalized

concentration of (a)substrate Fs , normalized
(b)oxygen
concentration
of
(c)
Fo and
mediator
clear that when the normalized parameter Bs

of mediator Fm increases for some fixed values of Bs ,
Fm
normalized
versus
Figure.5 is the normalized concentrations of

(a)substrate Fs , (b)oxygen Fo and (c) mediator Fm
versus the normalized distance x. From Figs. 5 (a) and
(c) it is clear that when the normalized parameter Bm
of substrate Fs and mediator Fm decreases for some
fixed values of Bs , Bo when 2s = 1 and m2 = 1. Figure.
5 (b) it is clear that when the normalized parameter Bm
increases,
the
corresponding
normalized
concentrations of oxygen Fo increases for some fixed
values of Bs , Bo and o2 = 1 .
Figure.6 is the normalized concentrations of the
substrate Fs , oxygen Fo and the mediator Fm versus the
Results and Discussions
of
versus the normalized distance x. From Fig. 4 (a)-(b) it

is clear that when the normalized parameter Bo
Bm and m2 = 1 .
Numerical Simulation
concentration
Figure4 is the normalized concentrations of

the
normalized distance x. From Fig.2 (a), (b) and (c) it is

clear that when the thiele modulus s2 , o2 and m2
increases,
the
corresponding
normalized
concentrations of substrate Fs , oxygen Fo , mediator
Fm decreases for some fixed values of the normalized
surface concentrations of the substrate Bs , normalized
dimensionless distance x . From this figure, we note

that the substrate, oxygen and mediator increasesfor
some fixed values of the parameters Bs , Bo , Bm and
2
2
2
=
=
=
1 Figure.7 is the variation of normalized
s
o
m
current J OX with (a) normalized thiele modulus m2 for

the mediator (b) normalized surface concentration of
the substrate Bs (c) normalized surface concentration
of oxygen Bo and (d) normalized surface concentration
of mediator Bm . From these Figs. 7 (a), (c) and (d) the
normalized current decreases and (b) increases for
some fixed values.
surface concentration of oxygen Bo and normalized

surface concentration of the mediator Bm respectively.
Figure3 is the normalized concentrations of
versus the normalized distance x. From Fig. 3 ((a)-(c))
we infer that when the normalized parameter Bs
FIGURE 1: GEOMETRY OF THE PROBLEM
35
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(a)
(b)
(a)
(b)
(c)
(c)
FIGURE 3: NORMALIZED CONCENTRATIONS OF (A)

SUBSTRATE Fs (EQN. (18)) (B) OXYGEN Fo (EQN.(19)) AND
(C)MEDIATOR Fm (EQN. (20)) COMPUTED FOR SOME FIXED
VALUES OF THE PARAMETERS B = 0.5 , Bo = 0.05 , Br = 0.1
s
AND VARIOUS VALUES OF THIELE MODULUS s2 , o2 AND m2 .
36

VALUES OF THE PARAMETERS Bo = 0.05 , Br = 0.1 AND 2s = 1
AND VARIOUS VALUES OF NORMALIZED SURFACE
CONCENTRATION OF SUBSTRATE BS , WHEN (I) BS = 0.001 (II)
BS = 0.005 (III) BS = 0.01 (IV) BS = 0.05 (V) BS = 0.1 AND

(V) B = 0.5
s
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(a)
(a)
(b)
(b)
(c)
(c)


VALUES OF THE PARAMETERS B = 0.5 , AND = 1 AND

s
VARIOUS VALUES OF NORMALIZED SURFACE
CONCENTRATION OF OXYGEN WHEN, (I) Bo = 0.001 (II)
VALUES OF THE PARAMETERS B = 0.5 , Bo = 0.05 AND m2 = 1

s
AND VARIOUS VALUES OF NORMALIZED SURFACE
CONCENTRATION OF MEDIATOR(II) Bm = 0.005 (III) Bm = 0.01
Bo = 0.05 (III) Bo = 0.1 (IV) Bo = 0.5 (V) Bo = 1 AND (VI) Bo = 2 .
(IV) Bm = 0.05 (V) Bm = 0.1 (VI) Bm = 0.2 AND (VI) Bm = 0.5 .
2
o
37
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(c)
FIGURE6: NORMALIZED CONCENTRATIONS OF SUBSTRATE

Fs (EQN. (18)) VERSUS THE NORMALIZED DISTANCE x ,
OXYGEN Fo (EQN. (19))VERSUS THE NORMALIZED DISTANCE
(d)
x WHEN B = 0.5 , Bo = 0.05 , Bm = 0.1 AND o2 = 1 AND

s
MEDIATOR Fm (EQN.(20)) VERSUS THE NORMALIZED
DISTANCE x WHEN B = 0.5 , Bo = 0.05 , Bm = 0.1 AND m2 = 1 .
s
(a)
FIGURE7: VARIATION OF NORMALIZED CURRENT J OX WITH

(A) NORMALIZED THIELE MODULUS FOR THE MEDIATOR (B)
NORMALIZED SURFACE CONCENTRATION OF THE
(b)
SUBSTRATE Bs (C) NORMALIZED SURFACE CONCENTRATION

OF OXYGEN Bo AND (D) NORMALIZED SURFACE
CONCENTRATION OF MEDIATOR Bm .
Conclusions
The system of non-linear reaction diffusion equations
of the model has been solved analytically. The
approximate
analytical
expressions
for
the
concentrations of substrate, oxygen, mediator and the
current at the enzyme-membrane electrode geometry
are obtained using the new Homotopy perturbation
method. This analytical result is useful for
improvingthe sensor design. The extension of the
procedure to the model with reduced mediator in the
bulk solution seems possible. These analytical
expressions can be used for the optimization of the
38
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thickness of the enzyme layer or Thiele modulus

which produces significant change in both the
magnitude of the current and the general behavior of
the system.
Setting p = 1 results in the approximate solution of

the eqn. (A.1):
(A.9)
u = lim v = v0 + v1 + v2 + ...
ACKNOWLEDGEMENT
p 1
The authors are thankful to the Secretary, the Principal

and the Head of the Department of Mathematics, The
Madura College, Madurai, India for their constant
encouragement.
Appendix A: Basic Concept of the Homotopy
Perturbation Method
To explain this method, let us consider the following
function:
Do (u ) =
f (r ) 0,
(A.1)
with the boundary conditions of

u
Bo =
(u ,
) 0,
n
(A.2)
where Do is a general differential operator, Bo is a

boundary operator,
(A.8)
v =v0 + pv1 + p 2 v2 + ...
f (r ) is a known analytical
function and is the boundary of the domain . In

general, the operator Do can be divided into a linear
part L and a non-linear part N . The eqn.(A.1) can
therefore be written as
L(u ) + N (u ) f (r ) =
0
(A.3)
By the Homotopy technique, we construct

Homotopy v(r , p ) : [0,1] that satisfies
H (v, p ) =
(1 p )[ L(v) L(u0 )] + p[ Do (v) f (r )] =
0 (A.4)
H (v, p ) =L(v) L(u0 ) + pL(u0 ) + p[ N (v) f (r )] =0 (A.5)
where p [0, 1] is an embedding parameter, and u0 is

an initial approximation of the eqn.(A.1) that satisfies
the boundary conditions. From the eqns. (A.4) and
(A.5), we have
H (v, 0) =L(v) L(u0 ) =0
(A.6)
H (v,1) = Do (v) f (r ) = 0
(A.7)
When p=0, the eqns.(A.4) and (A.5) become linear

equations. When p =1, they become non-linear
equations. The process of changing p from zero to
unity is that of L(v) L(u0 ) =
0 to Do (v) f (r ) =
0 . We
first use the embedding parameter p as a small
parameter and assume that the solutions of the eqns.
(A.4) and (A.5) can be written as a power series in p :
This is the basic idea of the HPM.

Appendix B: Analytical Solution of the
System of Non-linear Equations (12)-(16)
Using New Homotopy Perturbation
Method [16-27]
In this Appendix, we indicate how the eqns. (18)-(20)
in this paper is derived. To find the solution of the
eqns.(12) - (14), we construct the new Homotopy as
follows:
2
2
d Fs s ( Fo (1) Bo + Fm (1) Bm ) Fs (1) Bs
(1 p ) 2
dx
( Fo (1) Bo + Fm (1) Bm ) Fs (1) Bs + Fs (1) Bs
+ ( F (1) B + F (1) B )
o
o
m
m
(B.1)
2
( Fo Bo + Fm Bm ) Fs Bs
d Fs
2
0
+ p 2 s
=
dx
( Fo Bo + Fm Bm ) Fs Bs + Fs Bs
+(F B + F B )
o o
m m
d 2F
s2 ( Bo + Bm ) Bs
(1 p ) 2s
( Bo + Bm ) Bs + Bs + ( Bo + Bm )
dx
d 2 Fs
dx
=
+p
0 (B.2)
2
( Fo Bo + Fm Bm ) Fs Bs
s
+(F B + F B )
o o
m m
d 2 Fo
2
dx

(1 p )

o2 Fo (1) Bo Fs (1) Bs

+ F (1) B + F (1) B
o
m
m)
( o
d 2F
+ p 2o o2
dx
Fo Bo Fs Bs
F B +F B F B +F B
m m) s s
s s
( o o
+(F B + F B )
o o
m m
(B.3)
0
=
39
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d 2F
d 2 ( Fs + pFs + p 2 Fs + ...)
o2 Bo Bs
(1 p ) 2o
2
( Bo + Bm ) Bs + Bs + ( Bo + Bm )
dx
dx
d Fo
dx
(B.4)
=
+p
0
Fo Bo Fs Bs
( Fo + pFo + p Fo + ...) Bo
o
+
+
F
B
F
B
F
B
F
B
m m) s s
s s
( o o
+( F + pF + p 2 F + ...) B
+(F B + F B )
m
m
m
m

o o
m m
+p
( F + pF + p 2 F + ...) B
= 0
s
s
s
s
2
d 2 Fm
s
2
( Fo + pFo + p Fo + ...) Bo
2

dx

(
...)
F
pF
p
F
B
+
+
+
+
m
m
m
m

2
(1 p )
( Fs + pFs + p Fs + ...) Bs

m2 Fm (1) Bm Fs (1) Bs
+ ( Fs + pFs + p Fs + ...) Bs
+ F (1) B + F (1) B
(
)
( F + pFo + p Fo + ...) Bo
o
o
m
m
+ o
(B.5)
2
2
(B.10)
+( Fm + pFm + p Fm + ...) Bm
d Fm
dx
Substituting the eqns. (B.7)-(B.9) into an eqn.(B.4) we get
=
+p
0
2
d 2 ( Fo + pFo + p 2 Fo + ...)
Fm Bm Fs Bs
2
dx
(1 p )
2
+(F B + F B )
o Bo Bs
o o
m m
( Bo + Bm ) Bs + Bs + ( Bo + Bm )
d 2F
m2 Bm Bs
d 2 ( Fo + pFo + p 2 Fo + ...)
(1 p ) 2m
(
)
(
)
+
+
+
+
B
B
B
B
B
B
dx
o
m
s
s
o
m
dx 2
d 2 Fm
dx
(B.6)
+p
=
0
Fm Bm Fs Bs
+
+
F
B
F
B
F
B
F
B
(
)
o
o
m
m
s
s
s
s
( F + pF + p F + ...) B
+(F B + F B )
o
o
o
o
o o
m m
+p
( F + pF + p 2 F + ...) B
= 0
s
s
s
s
2
The analytical solution of the eqn.(B.2) is

o
2
F
pF
p
F
B
(
...)
+
+
+
o
o
o
o
(B.7)
Fs =Fs0 + pFs1 + p Fs2 + ..........
+( Fm + pFm + p 2 Fm + ...) Bm
Similarly the analytical solutions of the eqns. (B.4) and

( F + pF + p 2 F + ...) B
s
s
s
s
(B.6) are
2
+( F + pF + p F + ...) B
s
s
s
s
2
(B.11)
(B.8)
Fo =Fo + pFo 1 + p Fo 2 +..........
0
( Fo + pFo + p Fo + ...) Bo
+( F + pF + p 2 F + ...) B
Fm =Fm0 + pFm1 + p 2 Fm 2 + ..........
m
m
m
m
(B.9)
0
Substituting the eqn.(B.7)-(B.9)into an eqn.(B.2) we get
Substituting the eqns.(B.7)-(B.9) into an eqn.(B.6) we get
d 2 ( Fs + pFs + p 2 Fs + ...)
dx 2
(1 p )
s2 ( Bo + Bm ) Bs
( Bo + Bm ) Bs + Bs + ( Bo + Bm )
d 2 ( Fm + pFm + p 2 Fm + ...)
2
dx
(1 p )
m2 Bm Bs
( Bo + Bm ) Bs + Bs + ( Bo + Bm )
40
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d 2 ( Fm + pFm + p 2 Fm + ...)
dx 2
( F + pF + p 2 F + ...) B
m
m
m
m
+p
( F + pF + p 2 F + ...) B
= 0
2
s
s
s
s
2
( F + pFo + p Fo + ...) Bo
+( Fm + pFm + p 2 Fm + ...) Bm
( Fs + pFs + p Fs + ...) Bs
+ ( F + pF + p 2 F + ...) B
s
s
s
s
2
( F + pF + p F + ...) B

o
o
o
+ o
+( F + pF + p 2 F + ...) B
m
m
m
m
(B.12)

Fo =
(1) 0; F 'o (0)
= 0=
, i 1, 2,3,...
i
Comparing the coefficients of like powers of p in (B.10)
Fo ( x)= Fo =
0
k22 2
( x 1) + 1
2
(B.20)
Where k22 is defined in the text eqn.(22).

After putting the eqn.(B.20) into an eqn.(B.8), we
obtain the solution in the text eqn.(19).
Comparing the coefficients of like powers of p into an
eqn.(B.12) we get
p0 :
d 2 Fm
dx 2
Bm Bs
0 (B.21)
m2
=
B
B
B
B
B
B
+
+
+
+
(
)
(
)
m
s
s
o
m
o
The initial approximations are as follows:

=
Fm (1) 1;=
F 'm (0) 1
we get
(B.19)
Solving the eqn. (B.17) and using the boundary

conditions eqns. (B.18)-(B.19), we obtain the following
result:
(B.22)
( Bo + Bm ) Bs
(B.23)
=
Fm (1) 0;=
F 'm (0) 0
s2
0 (B.13)
=
dx
( Bo + Bm ) Bs + Bs + ( Bo + Bm )
Solving the eqn.(B.21) and using the boundary
The initial approximations are as follows
conditions eqns.(B.22)-(B.23), we obtain the following
result:
(B.14)
=
F (1) 1;=
F ' (0) 0
p0 :
d Fs
s0
s1
(1) 0; F 's =
(0) 0=
, i 1, 2,3,...
Fs =
i
(B.15)
Solving the eqn. (B.13) and using the boundary

conditions eqns.(B.14)-(B.15), we obtain the following
result:
Fs ( x) = Fs =
0
Where
k12
k12 2
( x 1) + 1
2
(B.16)
is defined in the text eqn. (21).
After putting the eqn. (B.16) into an eqn. (B.7), we

Fm ( x) = Fm0 =
k32 2
( x x) + 1
2
(B.24)
Where k32 is defined in the text eqn. (23).

After putting the eqn.(B.24) into an eqn.(B.9), we
Appendix C: Scilab/Matlabprogram for the
Numerical Solution of the Systems of
Non-linear Differential Eqns. (12)-(16)
function pdex4
m = 0;
Comparing the coefficients of like powers of p intoan
x = linspace(0,1);
eqn.(B.11) we get
t = linspace(0,100000);
sol = pdepe(m,@pdex4pde,@pdex4ic,@pdex4bc,x,t);
2
d Fo
0
u1 = sol(:,:,1);
p :
dx 2
u2 = sol(:,:,2);
(B.17)
Bo Bs
2
u3 = sol(:,:,3);
0
o
=
B
B
B
B
B
B
(
+
)
+
+
(
+
)
%plot(x,u1(end,:))
m
s
s
o
m
o
%xlabel('Distance x')
The initial approximations are as follows
%ylabel('u1(x,2)')
%figure
(B.18)
=
Fo (1) 1;=
F 'o (0) 0
0
41
www.seipub.org/fs
%plot(x,u2(end,:))
%xlabel('Distance z')
%ylabel('u2(x,2)')
%figure
%plot(x,u3(end,:))
%xlabel('Distance x')
%ylabel('u3(x,2)')
% -------------------------------------------------------------function [c,f,s]=pdex4pde(x,t,u,DuDx)
c = [1;1; 1];
f = [1; 1; 1] .* DuDx;
Bs=0.5; B0=0.05; Br=0.1;
a1=sqrt(0.001); a2=sqrt(0.001); a3=sqrt(0.001);
F1 =-a1^2/(1+(1/(u(2)*B0+u(3)*Br))+(1/(u(1)*Bs)));
Appendix D: Nomenclature
Symbol
Meaning
Total active enzyme concentration in the matrix
(mmol/L)
Enzyme concentration of the oxidized mediator
(mmol/L)
[E ]
t
[E ]
OX
[ ES ]
[E ]
Enzyme concentration of the substrate (mmol/L)

Reduced enzyme concentration (mmol/L)
red
Concentration of oxygen at any position in the enzyme

layer (mmol/L)
[O ]
2
[O ]
[O ]
2 b
Oxygen concentration in the bulk electrolyte (mmol/L)
Oxygen concentration in the bulk solution (mmol/L)
[S ]
[S ]
[ MedOX ]
[ Med ]
OX
[ Med ]
OX
Concentration of substrate at any position in the

enzyme layer (mmol/L)
Substrate concentration in the bulk electrolyte
(mmol/L)
Concentration of oxidised mediator at any position in
the enzyme layer(mmol/L)
Oxidised mediator concentration in the bulk
electrolyte (mmol/L)
Oxidized mediator concentration in the bulk solution
(mmol/L)
F2 =(a2^2*(u(2)*B0)/(u(2)*B0+u(3)*Br))*(1/(1+(1/(u(2)*B0+u(
3)*Br))+(1/(u(1)*Bs))));
F3 =(a3^2*(u(3)*Br)/(u(2)*B0+u(3)*Br))*(1/(1+(1/(u(2)*B0+u(
3)*Br))+(1/(u(1)*Bs))));
s = [F1; F2; F3];
% -------------------------------------------------------------function u0 = pdex4ic(x)
u0 = [1; 1;1];
% -------------------------------------------------------------function [pl,ql,pr,qr] = pdex4bc(xl,ul,xr,ur,t)
pl = [0; 0; ul(3)-1];
ql = [1; 1; 0];
pr = [ur(1)-1; ur(2)-1; ur(3)-1];
qr = [0; 0; 0];
Greek Symbols
s2
Thiele modulus for the substrate (Normalized)
o2
Thiele modulus for the oxygen (Normalized)
Thiele modulus for the mediator (Normalized)
2
m
Subscripts
o
s
m
Oxygen
Substrate
Mediator
OX
Oxidized species
red
t
Reduced species
Total
Bulk solution
REFERENCES
Ananthaswamy V., and Rajendran L., Analytical solution

of two point non-linear boundary value problems in
Do
Diffusion coefficient of oxygen (cm2 s-1 )
Ds
Diffusion coefficient of substrate (cm2 s-1 )
Dm
Diffusion coefficient of mediator (cm2 s-1)
d
y
Enzyme layer thickness (cm)

Distance from the electrode (cm)
k1 , k4 , k5
Rate constants ( L mol-1 s-1 )
k 2 , k5
Rate constants ( s-1 )
Ko
Partitioning coefficient for oxygen (none)
Ks
Partitioning coefficient for substrate (none)
Km
Partitioning coefficient for mediator (none)
Bo
Normalized surface concentration of oxygen
Bs
Normalized surface concentration of the substrate
Bm
Normalized surface concentration of mediator
Approximate analytical solution of non-linear boundary
Fs
Normalized surface concentration
value problem of steady state flow of a liquid film:
Fo
Normalized oxygen concentration
Homotopy perturbation method. International Journal
Fm
Normalized mediator concentration
of Applied Science and Engineering Research. 2 (5)
42
porous catalyst particles. International Journal of

Mathematical Archive. 3(3) (2012): 810-821.
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of some two-point non linear elliptic-boundary value
problems. Applied Mathematics. 3 (2012): 1044-1058.
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Non-isothermal
diffusion-reaction
processes
and
effectiveness factors. ISRN Physical chemistry, Hindawi

publishing corporation. 2012 (2012): 1-14.
Ananthaswamy
V.,
Ganesan
SP.,
and
Rajendran.,
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responses
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J.J.,
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E.A.H.,
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glucose oxidase onto the blend membrane of poly (vinyl
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(1996): 131-138.
Li X.J., Liu Y.X., An Improved approach to nonlinear
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Schulmeister T., and Pfeiffer D., Mathematical modelling of
enzyme
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E., Halliwell C.M, Seng Toh C., Cass A.E.G, and P.N.
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Schulmeister T., Mathematical modeling of the dynamic

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Instrumentation
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He J.H., Homotopy perturbation technique. Comp. Meth.
lactate
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poly (anion) composite films. Preparation of bioanodes
for
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(2002): 13-15.
Trevan M.D., Immobilised enzymes, 2nd edn. Wiley, New
York, 1981.
Dr. V. Ananthaswamy received his
M.Sc. Mathematics degree from
The
Madura
College
(Autonomous),
Madurai-625011,
Tamil Nadu, India during the year
2000. He has received his M.Phil
degree in Mathematics from
Madurai
Kamaraj
University,
Madurai, Tamil Nadu, India
during the year 2002. He has
received his Ph.D., degree (Under the guidance of Dr. L.
43
www.seipub.org/fs
Rajendran, Assistant Professor, Department of Mathematics,

The Madura College, Tamil Nadu, India) from Madurai
Kamaraj University, Madurai, Tamil Nadu, India, during the
year October 2013. He has 14 years of teaching experiences
for Engineering Colleges, Arts & Science Colleges and
Deemed University. He has 3 years of research experiences.
At present he is working as Assistant Professor in
Mathematics, The Madura College (Autonomous), Madurai625 011, Tamil Nadu, India from 2008 onwards. He has
published more than 23 research articles in peer-reviewed
National and International Journals and communicated 7
research articles in National and International Journals.
Presently
he
has
Reviewer/Editorial
Board
Member/Advisory Board Member in 43 reputed National
and International Journals. Currently he has doing one
ongoing minor research project sanctioned at UGC. His
present research interest includes: Mathematical modeling
based
on differential equations
and
asymptotic
approximations, Analysis of system of non-linear reaction
diffusion equations in physical, chemical and biological
sciences, Numerical Analysis, Mathematical Biology,
Mathematical and Computational Modeling, Mathematical
Modeling for Ecological systems. Also, he has participated
and presented research papers in National and International
Conferences.
Mrs. M. Subha received her M.Sc.,degree
(2012) and M.Phil., degree (2013) in
Mathematics from The Madura College
and E.M.G. Yadhava Womens College,
Madurai, Tamilnadu, India. At present,
She is working as Assistant Professor in
the Department of Mathematics, Madurai
44
Sivakasi Nadars Pioneer Meenakshi Womens College,

Sivagangai District, Tamil Nadu, India. Also, she is doing
her Ph.D entitled Asymptotic Methods for Solving Initial
and Boundary Value Problems at Madurai Kamaraj
University, Madurai under the guidance of Dr. L. Rajendran,
Assistant Professor, Department of Mathematics, The
Madura College, Madurai. Her present research interest
include: Mathematical modelling, Analytical solution of
system of nonlinear reaction diffusion processes in
biosensor, Homotopy analysis method, Homotopy
perturbation and numerical methods. She has published 4
papers in International Journals and communicated one
research paper in National Journal. Also, She has
participated and presented research papers in International
and National Conferences.
Ms. C. Chowmiya received her M.Sc.,
degree in Mathematics from Sri
Meenakshi Government Arts and Science
College for Women (Autonomous),
Madurai, Tamil Nadu, India during the
year 2013. She has completed her M.Phil.,
(Mathematics) from The Madura College
(Autonomous), Madurai, Tamil Nadu,
India during the year2014. At present, She is working as
Assistant Professor in the Department of Mathematics, Syed
Ammal Engineering College, Ramanathapuram District,
Tamilnadu, India. She has presented a paper at National
Conference. She has published one National and
International Journals. Her research area includes;
Mathematical Modeling for solving Biosensor problems,
Solving Non-linear differential equations by Numerical and
Asymptotic Methods.

A Simple Analytical Expression of A Non-Linear Boundary Value Problem For An Immobilized Oxidase Enzyme Electrode Using The New Homotopy Perturbation Method

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A Simple Analytical Expression of A Non-Linear Boundary Value Problem For An Immobilized Oxidase Enzyme Electrode Using The New Homotopy Perturbation Method

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Frontiers in Sensors (FS) Volume 2, 2014