Вы находитесь на странице: 1из 19

Copyright 2014 by Modern Scientific Press Company, Florida, USA

International Journal of Modern Mathematical Sciences, 2014, 10(3): 201-219



I nternational J ournal of Modern Mathematical Sciences
Journal homepage:www.ModernScientificPress.com/Journals/ijmms.aspx
ISSN: 2166-286X
Florida, USA
Article
Approximate Analytical Expressions of Non-linear Boundary
Value Problem in an Amperometric Biosensor Using the New
Homotopy Perturbation Method
D. Shanthi
2
, V. Ananthaswamy
1
and L. Rajendran
1,
*
1
Department of Mathematics, The Madura College, Madurai-625011, Tamil Nadu, India
2
PG Assistant, Government Higher Secondary School, Podhumbu, Madurai, Tamil Nadu, India.

*Author to whom correspondence should be addressed
1
: raj_sms@rediffmail.com; Ph.No. 0452-
4208051, Mob. No. +91-9442228951.

Article history: Received 2 February 2014, Received in revised form 20 May 2014, Accepted 30 May
2014, Published 6 June 2014.


Abstract: A theoretical model of modified enzyme-membrane electrode forsteady-state
condition is discussed. This model contains a non-linear term related to enzyme kinetics
reactions. The closed and simple approximate analytical expressionsofthe concentrations of
the species and current are obtained by new approach of Homotopy perturbation method.
These expressions are derived for all possible values of parameters
2
| (Thiele modulus),
0
B
(normalized surface concentration of oxidized mediator) and
S
B (normalized surface
concentration of substrate). The theoretical results thus obtained were then verified by the
numerical results. A good agreement between theoretical predictions and numerical results
is observed.

Keywords Enzyme-membrane; Permeable electrode; Immobilised enzyme layer; Biosensor;
Numerical Simulation; New Homotopy perturbation method.

Mathematics Subject Classifications (2000): Mathematical Modeling and non-linear
differential equation.

Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
202
1. Introduction
Polymer membranes have been utilized in biomaterials, bio-separators and biosensors [1-2]. 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 [3]. Recently a new method for enzyme immobilization [4] has been successfully used
for the building of enzymatic bio-sensors and also of a chemically active membrane [5]. In the recent
three decades, much effort has been devoted to the development of various biosensors involving
biologically sensitive component and transformers - devices with many fields of applications [6-8].
Atwo-substrate non-linear enzyme reaction model has been developedexperimentally [9-10]. The
behaviour of a glucose oxidize (GOx) electrode [11-12] is discussed in this model. It has been found that
the mediators could not totally replace the natural co-substrate when both were present in the assay
solution. So that here, a three-substrate model would be required. In these cases, various complex
calibration curve of the enzyme electrode was observed [13-14].
Inspite of extensive experimental investigations for the design of bio-sensor, only a few studies
concerned the modeling or theoretical design of such system. Loghambal and Rajendran [15] have
described the mathematical model in an amperometric oxidase enzyme-membrane electrode. Simulation
results for amperometric enzyme electrode [16-18] reported using Runge-Kutta method [16]and
shooting method [17-18]. But in this paper, the same system is modeled analytically. However, to the
best of our knowledge, till date no general simple analytical results for the concentration of oxidized
mediator, substrate and reduced mediator for all values of the parameters have been reported [17-19].
The purpose of this communication is to derive the closed-form of analytical expressions of
concentrations of mediator, substrate and reduced mediator by solving the system of non-linear reaction-
diffusion equations using the New Homotopy perturbation method [34-35]. The theoretical models of
enzyme electrodes give information about the mechanism and kinetics operating in the biosensor. This
theoretical results gained from this modeling can be useful in sensor design, optimization and prediction
of the electrode-membranes response.

2. Mathematical Formulation of the Problems
Gooding and Hall [17] presented a concise discussion and derivation of the dimensionless non-
linear mass transport equation for this model, which is summarized briefly for completeness. In this
model the substrate and co-substrate penetrate through a permeable electrode to the enzyme layer and
then reduces to the form of co-substrate which diffuses back to the electrode. The general reaction
scheme for an immobilized oxidase in the presence of two oxidants is given as follows [17]:
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
203

where
m
k is the rate constant for the forward direction of the m
th
reaction and
1
k is the rate constant for
the backward direction. If ] E [
T
is the total enzyme concentration in the matrix then at all times,
] [E ES] [ ] E [ ] [E
red OX T
+ + = (4)
where ] E [
OX
, ] ES [ and ] [E
red
are the oxidized mediator, enzyme-substrate complex and reduced
mediator enzyme concentrations respectively. At steady state, the diffusion of a substrate into the
enzyme layer is equal to the reaction rate of the substrate within the matrix. We examine a planar matrix
of thickness y = d, where diffusion is considered in the y- direction only (edge effects are neglected)
(Fig.1).


Fig. 1.Schematic representation of typical enzyme-membrane electrode geometry [17].
The system of non-linear differential equations for this scheme is given as follows [17]:
1
OX
O S
T 2
2
OX
2
M
1
] [Med [S]
] [E
dy
] Med [ d

|
|
.
|

\
|
+ + ==
| |
k D (5)
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
204
1
OX
O S
T 2
2
2
S
1
] [Med [S]
] [E
dy
] S [ d

|
|
.
|

\
|
+ + ==
| |
k D (6)
1
OX
O S
T 2
2
red
2
M
1
] [Med [S]
] [E
dy
] Med [ d

|
|
.
|

\
|
+ + ==
| |
k D (7)
where
M
D is the diffusion coefficient of the oxidized and reduced forms of the mediator (assumed to be
equal) and
S
D is the diffusion coefficient of substrate within the enzyme layer. ] Med [
OX
, ] Med [
red
and
S] [ are the concentration of oxidized mediator, reduced mediator and substrate at any position in the
enzyme layer.
S
| and
O
| are the dimensionless rate constants
(
1 2 1 S
/ ) ( k k k + =

| and
4 2 O
/ k k = | ). The Eqns. (5)-(7) are solved for the following boundary
conditions:
At the far wall, y = 0
0 dy ] Med [ d dy / ] S [ d dy ] Med [ d
red OX
= = = (8)
at the electrode, y = d
0 ] Med [ , ] [S ] S [ ] S [ , ] Med [ ] Med [ ] Med [
red S b OX O b OX OX
= = = = =

K K (9)
b OX
] Med [ and
b
] S [ are the concentration of oxidized mediator and substrate at the enzyme layer|
electrode boundary, and

] Med [
OX
and

] [S are the bulk solution concentrations.


O
K

and
S
K are the
equilibrium partition coefficients for oxidized mediator and the substrate respectively. We make the
non-linear differential eqns. (5)-(7) to dimensionless form by defining the following dimensionless
variables,
] [S ] [Med and ] Med [ ] E [
, ] S [ , ] Med [ , y
, ] Med [ ] Med [ , ] S [ ] S [ , ] Med [ ] Med [
b S b OX M S b OX M T 2
2 2
S b S 0 b OX 0
b red red R b S b OX OX 0
D D D k d
B B d x
F F F
= =
= = =
= = =
|
| | (10)
where
O
F ,
S
F and
R
F are the normalized surface concentrations of oxidized mediator, substrate and
reduced mediator and x is the normalized distance.
O
B

and
S
B are the normalized surface concentration
of oxidized mediator and substrate.
2
| is the Thiele modulus for the oxidized mediator which governs
reaction/diffusion. The dimensionless form of the oxidized mediator, substrate and reduced mediator are
as follows:
(

+ +
=
S 0 S 0 S S 0 0
S 0 S 0 2
2
0
2
F F B B F B F B
F F B B
dx
F d
| (11)
(

+ +
=
S 0 S 0 S S 0 0
S 0 S 0 2
S
2
S
2
F F B B F B F B
F F B B
dx
F d
| (12)
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
205
(

+ +
=
S 0 S 0 S S 0 0
S 0 S 0 2
2
R
2
F F B B F B F B
F F B B
dx
F d
| (13)
The consumption of oxidized mediator, substrate and reduced mediator, are all related processes. So
there is only one independent variable for which to solve
(

+ +
= = =
S 0 S 0 S S 0 0
S 0 S 0 2
2
R
2
2
S
2
S
2
0
2
1
F F B B F B F B
F F B B
dx
F d
dx
F d
dx
F d
|

(14)
The normalized boundary conditions are given by:
0 ) 0 (
'
0
= F 0 ) 0 (
'
S
= F 0 ) 0 (
'
R
= F (15)
1 ) 1 (
0
= F 1 ) 1 (
S
= F 0 ) 1 (
R
= F (16)
From the eqn. (14) we get,
2
0
2
2
S
2
S
1
dx
F d
dx
F d
=

(17)
and
2
R
2
2
S
2
dx
F d
dx
F d
S
= (18)
Integrating the eqns. (17) and (18) twice and applying the appropriate boundary conditions eqns. (15)
and (16) we get,
| | ) 1 ) ( ( ) / 1 ( 1 ) (
S 0
+ = x F x F
S

(19)
| | ) ( 1 ) / 1 ( ) (
R
x F x F
S S
= (20)
The corresponding normalized current response is given by
1
R
=
|
.
|

\
|
=
x
dx
dF
I (21)
3. Analytical Expression of the Normalized Surface Concentrations Using 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 Homotopyperturbation method (HPM) [20-33] 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.
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
206
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 [20-23]. Recently this method
is also used to solve some of the non-linear problem in physical sciences [24-26]. This method is a
combination of Homotopy in topology and classic perturbation techniques. Ji-Huan He used to solve the
Lighthill equation [24], the Diffusion equation [25] and the Blasius equation [26-27]. The HPM is unique
in its applicability, accuracy and efficiency. The HPM [18-33] and New HPM [34-35] uses the
imbedding parameter p as a small parameter, and only a few iterations are needed to search for an
asymptotic solution.The analytical expression of concentration (see Appendix B) of the substrate is as
follows:
(

=
A
Ax
x F
cosh
cosh
) (
S
(22)
Using the eqn. (22), we can obtain the concentrations of oxidized mediator
0
F and reduced mediator
R
F from the eqns. (19) and (20).
1
cosh
cosh 1
1 ) (
0
(

+ =
A
Ax
x F
S

(23)

cosh
cosh
1
1
) (
R
(

=
A
Ax
x F
S

(24)
From the eqns. (21) and (24) we get the dimensionless current is as follows:
hA A I
S
tan
1

= (25)
where
S S
S s
B B B B
B B
A
0 0
0
0
+ +
=

| (26)

4. Numerical Simulation
The non-linear diffusion equations (eqns. (11)-(13)) 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 analytical solutions in Figs. 2 -5.

Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
207

Fig. 2. Normalized concentrations of (a) Oxidized mediator
0
F (eqn. (23)) (b) Substrate
S
F (eqn.(22))
and (c) Reduced mediator
R
F (eqn. (24)) computed for some fixed values of the dimensionless
parameters 05 . 0 , 0052 . 0 , 1 . 0
S S O
= = = B B and various values of thiele modulus
2
| .
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
208

Fig. 3. Dimensionless concentrations of (a) Oxidized mediator
O
F (eqn. (23)) (b) Substrate
S
F (eqn.
(22)) and (c) Reduced mediator
R
F (eqn.(24)) for some fixed values of parameters
25 and 5 . 0 , 1 . 0
2
S O
= = = | B and various values of normalized surface concentration of substrate
S
B
, when (i) 001 . 0
S
= B (ii) 005 . 0
S
= B (iii) 01 . 0
S
= B (iv) 05 . 0
S
= B (v) 1 . 0
S
= B and (vi) 1
S
= B .
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
209

Fig. 4. Dimensionless concentrations of (a) Oxidized mediator
O
F (eqn. (23)) (b) Substrate
S
F (eqn.
(22)) and (c) Reduced mediator
R
F (eqn.(24)) for some fixed values of parameters
100 , 05 . 0 , 0052 . 0
2
S S
= = = | B and various values of normalized surface concentration of oxidised
mediator
0
B when, (i) 001 . 0
0
= B (ii) 005 . 0
0
= B (iii) 01 . 0
0
= B (iv) 05 . 0
0
= B (v) 1 . 0
0
= B and (vi)
1
0
= B .
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
210


Fig. 5. Dimensionless concentrations of the Oxidized mediator
O
F (eqn. (23)), Substrate
S
F (eqn. (22))
and the Reduced mediator
R
F (eqn.(24)) versus the normalized distance x when
05 . 0 , 0052 . 0 , 1 . 0
S S O
= = = B B and 400
2
= |


Fig. 6. Variation of normalized current Iwith (a) normalized surface concentration of oxidized mediator
O
B ,(b)& (c)normalized surface concentration of the substrate
S
B (d) normalized parameter
S
for
various values of thiele modulus
2
| using eqn. (25), when (i) 50
2
= | (ii) 100
2
= | (iii) 200
2
= | (iv)
300
2
= | (v) . 400
2
= |
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
211
5. Results and Discussions
Fig. 1 is the Schematic representation of typical enzyme-membrane electrode geometry [17].
Fig. 2 is the normalized concentrations of (a) oxidized mediator
O
F , (b)substrate
S
F and (c) reduced
mediator
R
F versus the dimensionless distance x. From Fig. 2 (a) and (b), it is clear that when the thiele
modulus
2
| increases, the corresponding normalized concentrations of oxidized mediator
0
F and the
substrate
S
F decreases for some fixed values of ,
0 S
B B and .
S
From Fig. 2 (c), it is noted that when
the thiele modulus
2
| increases, the normalized concentrations of the reduced mediator
R
F also
increases for some fixed values of the surface concentrations of oxidized mediator
0
B and the substrate

S
B and the dimensionless parameter .
S

Fig. 3 is the normalized concentrations of (a) oxidized mediator
0
F , (b)substrate
S
F and (c)
reduced mediator
R
F versus the dimensionless distance x. From Fig. 3 (a) and (b), we infer that when the
dimensionless parameter
0
B increases, the corresponding the corresponding surface concentrations of
oxidized mediator
0
F and the substrate
S
F decreases for some fixed values of the dimensionless
parameters ,
2
S
| B and .
S
From Fig. 3(c), it is noted that when the dimensionless parameter
0
B
increases, the normalized surface concentrations of the reduced mediator
R
F also increases for some
fixed values of the dimensionless parameters ,
2
S
| B and .
S

Fig. 4 is the normalized concentrations of (a) oxidized mediator
O
F , (b)substrate
S
F and (c)
reduced mediator
R
F versus the dimensionless distance x. From Fig. 4 (a) and (b), we infer that when the
dimensionless parameter
S
B increases, the corresponding the corresponding concentrations of oxidized
mediator
0
F and the substrate
S
F decreases for some fixed values of the dimensionless parameters
,
2
0
| B and .
S
From Fig. 4(c), it is noted that when the dimensionless parameter
S
B increases, the
normalized concentrations of the reduced mediator
R
F also increases for some fixed values of the
dimensionless parameters ,
2
0
| B and .
S


Fig. 5 is the normalized concentrations of the oxidized mediator
0
F , substrate
S
F and the reduced
mediator
R
F versus the dimensionless distance x . From this figure, we note that the oxidized mediator
and the substrate increases and the reduced mediator decreases for some fixed values of the
dimensionless parameters , ,
2
0
|
S
B B and .
S


Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
212
The normalized current I can be calculated using the eqn. (25). Fig. 6 is the normalized current I
versus (a) the normalized surface concentrations of the oxidized mediator
0
F , (b) &(c) the normalized
surface concentrations of the substrate
S
F and (d) the normalized parameter
S
. From these figures, it
is clear that the normalized current increases for various values of the dimensionless parameters
2
| .
6. Conclusions
The non-linear reaction diffusion equationsin an amperometric biosensor was solved analytically.
The approximate analytical expressions for the steady state concentrations of oxidised mediator,
substrate and reduced mediator for all values of parameters
2
| ,
O
B and
S
B at the enzyme-membrane
electrode geometry are obtained using the new Homotopy perturbation method. A satisfactory agreement
with the numerical simulation result is noted. These analytical expressions can be used to analyze the
effect of different parameters such as membrane thickness, type of buffer in the external solution and
enzyme loading in the membrane. This theoretical result is also useful for the optimize the sensitivity of
the bio-sensor.

Acknowledgements
This work was supported by the Council of Scientific and Industrial Research (CSIR No.:
01(2442)/10/EMR-II), Government of India. The authors are also thanks to the Secretary Shri. S.
Natanagopal, Madura College Board, Madurai, and Dr. R. Murali, The Principal, The Madura College,
Madurai, Tamilnadu, India for their constant encouragement.

References
[1] Simon, E., Halliwell, C. M., SengToh, C., Cass, A. E. G., Bartlett, P. N., Immobilisation ofenzymes
on poly(aniline)poly(anion) composite films. Preparation of bioanodes for biofuelcell
applications, Bioelectrochemistry, 55(2002): 13-15.
[2] Liu, Y., Zhang, X., Liu, H., Yu, T., Deng, I., Immobilization of glucose oxidase onto theblend
membrane of poly(vinyl alcohol) and regenerated silk fibroin: morphology and application to
glucose biosensor.J. Biotechnol., 46(1996): 131-138.
[3] Trevan, M. D., Immobilised enzymes, 2nd edn.,Wiley, New York, 1981
[4] Trong Nguyen, Q., Ping, Z., Nguyen, T., Rigal, P., Simple method for immobilization of bio-
macromolecules onto membranes of different types, J. Membr. Sci., 213(2003): 85-95.
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
213
[5] Bhardwaj, A., Lee, J., Glauner, K., Ganapathi, S., Bhattacharyya, D., Butterfield, D.A.,
Biofunctional membranes: an EPR study of active site structure and stability of papain non-
covalently immobilized on the surface of modified poly(ether) sulfone membranes through
theavidin-biotin linkage, J. Membr. Sci.,119(1996): 241-252.
[6] Guilbault, G. G., Immobilised enzymes and cells, in K. Mosbach (Ed.,), Methods inenzymology,
Academic press, New York, 1988.
[7] Robeson, L. M.,Correlation of separation factor versus permeability for polymeric membranes, J.
Membr. Sci., 62(1991): 165-185
[8] Gronda, A. M., Buechel1, S., Cussler, E. L., Mass transfer in corrugated membranes, J.Membr.
Sci., 165(2000): 177-187.
[9] Leypoldt, J. K., Gough, D. A., Theoretical evaluation of transient responses of an amperometric
enzyme electrode, Anal. Chem., 56(1984): 2896-2904.
[10] Gooding, J., Hall, E. A. H., Parameters Influential in the design of oxygen detectingenzyme
,ElectrodesElectroanalysis, 8(1996): 407-413.
[11] Ying, L., Kang, E. T., Neoh, K. G., Covalent immobilization of glucose oxidase on microporous
membranes prepared from poly(vinylidene fluoride) with grafted poly(acrylicacid) side chains,J.
Membr. Sci.,208(2002): 361-374.
[12] Turmanova, S., Trifonov, A., Kalaijiev, O., Kostov, G., Radiation grafting of acrylicacid
ontopolytetrafluoroethylene films for glucose oxidase immobilization and its application in
membrane biosensor, J. Membr. Sci., 127(1997): 1-7.
[13] Pallaeschi, G., Turner, A. P. F., Amperometrictetrathiafulvalene-mediated lactate electrodeusing
lactate oxidase absorbed on carbon foil, Anal. Chim. Acta, 234(1990): 459-463.
[14] Ohara, T. Y. , Rajagopalan, R., Hellcr, A., Glucose electrodes based on cross-linked bis(2,2'-
bipyridine) chloroosmium(+/2+) complexed poly(1-vinylimidazole) films,Anal. Chem., 65(1993):
3512-3517.
[15] Loghambal, S., Rajendran, L., Mathematical modeling in amperometric oxidase enzymemembrane
electrodes, J. Membr. Sci., 373(2011): 20-28.
[16] Martens, N., Hall, E. A. H., Model for an Immobilized Oxidase enzyme electrode in thepresence
of two oxidants, Anal. Chem., 66(1994): 2763-2770.
[17] Gooding, J. J., Hall, E. A. H., Practical and theoretical evaluation of an alternative geometryenzyme
electrode,J. Electroanal. Chem., 417(1996): 25-33.
[18] Gooding, J. J., Hammerle, M., Hall, E. A. H., An enzyme electrode with response independent of
the thickness of the enzyme layer, Sensors and Actuators B, 34(1996): 516-523.
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
214
[19] Loghambal, S., Rajendran, L., Mathematical modeling of a tubular spectrochemical cell using the
finite Hankel transformation, Russ. J. Electrochem., 47(2011): 883 - 889.
[20] Q.K. Ghori, M. Ahmed, and A. M. Siddiqui, Application of Homotopy perturbation method to
squeezing flow of a Newtonian fluid, Int. J. Nonlinear Sci.Numer. Simulat, 8(2007): 179-184.
[21] T. Ozis, and A. Yildirim, A Comparative study of Hes Homotopy perturbation methodfor
determining frequency-amplituderelation of a nonlinear oscillator with discontinuities,Int. J.
Nonlinear Sci. Numer.Simulat, 8 (2007): 243-248.
[22] S. J. Li, and Y. X. Liu, An Improved approach to non-linear dynamical systemidentification using
PID neural networks, Int. J. Nonlinear Sci. Numer. Simulat, 7(2006): 177-182.
[23] M. M. Mousa, S. F. Ragab, and Z. Nturforsch , Application of the Homotopyperturbation method
to linear and non-linear Schrdinger equations,. Zeitschrift fr Naturforschung, 63(2008): 140-144
[24] J.H. He, Homotopy perturbation technique, Comp Meth. Appl. Mech. Eng, 178(1999): 257-262.
[25] J. H. He, Homotopy perturbation method: a new nonlinear analytical technique, Appl.
Math.Comput, 135(2003): 73-79.
[26] J. H. He., A simple perturbation approach to Blasius equation, Appl. Math. Comput, 140(2003):
217-222.
[27] P.D. Ariel, Alternative approaches to construction of Homotopy perturbation algorithms,
Non-linear. Sci. Letts. A., 1(2010): 43-52.
[28] S. Loghambal and L. Rajendran, Mathematical modeling of diffusion and kinetics of amperometric
immobilized enzyme electrodes, ElectrochimActa, 55(2010):5230-5238.
[29] A. Meena and L Rajendran, Mathematical modeling of amperometric and potentiometricbiosensors
and system of non-linear equations Homotopy perturbation approach, J. ElectroanalChem,
644(2010): 50-59
[30] V. Ananthaswamyand L. Rajendran, Analytical solution of two-point non-linear boundaryvalue
problems in a porous catalystparticles, International Journal of Mathematical Archive, 3(3)(2012):
810-821.
[31] V. Ananthaswamy and L. Rajendran, Analytical solutions of some two-point non-linearelliptic
boundary value problems, Applied Mathematics,3(2012): 1044-1058.
[32] V. Ananthaswamy and L. Rajendran, Analytical solution of non-isothermal diffusion-reaction
processes and effectiveness factors, ISRN- Physical Chemistry, Article ID 487240, 2012(2012): 1-
14.
[33] V. Ananthaswamy, SP. Ganesan and L. Rajendran, Approximate analytical solution ofnon-linear
boundary value problem of steady state flow of a liquid film: Homotopyperturbation method,
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
215
International Journal of Applied Science and Engineering Research (IJASER), 2(5) (2013): 569-
577.
[34] L. Rajendran and S. Anitha, Comments on analytical solution of amperometricenzymatic
reactions based on Homotopy perturbation method by Ji-Huan He, Lu-Feng Mo,Electrochim.
Acta,102 (2013): 474-476.
[35] D. Shanthi, V. Ananthaswamy and L. Rajendran, Analysis of non-linear reaction-diffusionequations
with Michaelis - Menten kinetics by a new Homotopyperturbation, Natural Science, 5 (9)(2013):
1034-1046.


Appendix A
Basic concept of the Homotopy perturbation method[20-35]
To explain this method, let us consider the following function:
r , 0 ) ( ) ( O e = r f u D
o
(A.1)
with the boundary conditions of
r , 0 ) , ( I e =
c
c
n
u
u B
o
(A.2)
where
o
D is a general differential operator,
o
B is a boundary operator, ) r ( f is a known analytical
function and I is the boundary of the domain O. In general, the operator
o
D can be divided into a
linear part L and a non-linear part N . Equation (A.1) can therefore be written as
0 ) ( ) ( ) ( = + r f u N u L (A.3)
By the Homotopy technique, we construct a Homotopy 9 O ] 1 , 0 [ : ) , ( p r v that satisfies
0 )] ( ) ( [ )] ( ) ( )[ 1 ( ) , (
0
= + = r f v D p u L v L p p v H
o
(A.4)
0 )] ( ) ( [ ) ( ) ( ) ( ) , (
0 0
= + + = r f v N p u pL u L v L p v H (A.5)
where pe[0, 1] is an embedding parameter, and
0
u is an initial approximation of the eqn.(A.1) that
satisfies the boundary conditions. From the eqns. (A.4) and (A.5), we have
0 ) ( ) ( ) 0 , (
0
= = u L v L v H (A.6)
0 ) ( ) ( ) 1 , ( = = r f v D v H
o
(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 0 ) ( ) (
0
= u L v L to 0 ) ( ) ( = r f v D
o
.
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 :
...
2
2
1 0
+ + + = v p pv v v (A.8)
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
216
Setting 1 = p results in the approximate solution of eqn. (A.1):
... lim
2 1 0
1
+ + + = =

v v v v u
p
(A.9)
This is the basic idea of the HPM.

Appendix B
Analytical solution the normalized concentration of the substrate (eqn.(12)) using New Homotopy
perturbation method
In this Appendix, we indicate how the eqn. (22) in this paper is derived. To find the solution of eqns.(11)
- (13) we construct the new Homotopy as follows [24-25]:
0
) 1 ( ) 1 ( ) 1 ( ) 1 (
) 1 (
) 1 (
S 0 S 0 S S 0 0
S 0 S 0 2
S
2
S
2
0 0 0 0
0 0
2
2
2
=
(
(

+ +
+
(
(

+ +

F F B B F B F B
F F B B
dx
F d
p
F F B B F B F B
F F B B
dx
F d
p
S S S S
S S S S
|
|
(B.1)
0 ) 1 (
S 0 S 0
S 0 S 0 2
S
2
S
2
0 0
0
2
2
2
=
(
(

+ +
+
(
(

+ +

B B B B
F F B B
dx
F d
p
B B B B
F B B
dx
F d
p
S S
S S S S
|
|
(B.2)
The analytical solution of the eqn.(B.2) is
..........
2
2
1
0
+ + + =
S S S S
F p pF F F (B.3)
Similarly the analytical solutions of eqns. (11) and (13) be
..........
2 0
2
1 0 0 0
0
+ + + = F p pF F F
(B.4)
..........
2
2
1
0
+ + + =
R R R R
F p pF F F
(B.5)

Substituting (B.3) -(B.5) in (B.2) we get
0
....) ...)( (
...) ( ....) (
.....) ....)( (
.....) (
....) ( ...) (
) 1 (
2 0
2
1 0 0 2
2
1 S 0
2
2
1 S 2 0
2
1 0 0 0
2
2
1 2 0
2
1 0 0 S 0
2
S
2
2
2
1
2
0 0
2
2
1 0
2
2
2
2
1
2
0 0
0 0
0 0
0
0 0
=
(
(
(
(
(
(
(
(
(

(
(
(
(
(
(

+ + + + + +
+ + + + + + + +
+ + + + + +

+ + +
+
(
(

+ +
+ + +

+ + +

F p pF F F p pF F B B
F p pF F B F p pF F B
F p pF F F p pF F B B
dx
F p pF F d
p
B B B B
F p pF F B B
dx
F p pF F d
p
S S S
S S S
S S S
S S S
S S
S S S S S S S S
|
|
(B.6)
Comparing the coefficients of like powers of p in the eqn.(B.6) we get

0 :
S 0 S 0
0 S S 0 2
S
2
0 S
2
0
=
(

+ +

B B B B
F B B
dx
F d
p | (B.7)
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
217
The initial approximations is as follows
0 ) 1 ( , 1 ) 0 (
'
= =
i i
S S
F F (B.8)
0 ) 1 ( , 1 ) 0 (
'
= =
i i
S S
F F , ...... 3 , 2 , 1 = i (B.9)
Solving the eqns.(B.7) and using the boundary conditions (B.8)-(B.9), we obtain the following results:
) cosh(
) cosh(
) (
0
S
A
Ax
F x F
S
= = (B.10)
where A is defined in the text eqn. (26).
After putting the eqn. (B.10) into an eqn. (B.3), we obtain the solution in the text eqn.(22). Substituting
the eqns. (22) into an eqns. (19) and (20), we obtain the solutions in the text eqns. (23) and (24)

Appendix C
Scilab/Matlabprogram for the numerical solution of the systems of non-linear eqns. (11)-(13) and
(15)-(16).
function pdex 4
m = 0;
x = linspace(0 ,1);
t = linspace(0,100000);
sol = pdepe(m,@pdex4pde,@pdex4ic,@pdex4bc,x,t);
u1 = sol(:,:,1);
u2 = sol(:,:,2);
u3 = sol(:,:,3);
figure
%plot(x,u1(end,:))
xlabel('Distance x')
ylabel('u1(x,2)')
figure
plot(x,u2(end,:))
xlabel('Distance x')
ylabel('u2(x,2)')
figure
%plot(x,u3(end,:))
xlabel('Distance x')
ylabel('u3(x,2)')
% --------------------------------------------------------------
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
218
function [c,f,s] = pdex4pde(x,t,u,DuDx)
Bs=.0052;
B0=01;
A=sqrt(225);
us=0.05;
up=1;
c = [1;1; 1];
f = [1; 1; 1] .* DuDx;
F1 =-A^2*((B0*Bs*u(1)*u(2)/(B0*u(1)+Bs*u(2)+B0*Bs*u(1)*u(2))));
F2 =-us*A^2*((B0*Bs*u(1)*u(2)/(B0*u(1)+Bs*u(2)+B0*Bs*u(1)*u(2))));
F3 =up*A^2*((B0*Bs*u(1)*u(2)/(B0*u(1)+Bs*u(2)+B0*Bs*u(1)*u(2))));
s = [F1; F2; F3];
% --------------------------------------------------------------
function u0 = pdex4ic(x);
u0 = [1; 0; 1];
% --------------------------------------------------------------
function [pl,ql,pr,qr] = pdex4bc(xl,ul,xr,ur,t)
pl = [0; 0; 0];
ql = [1; 1; 1];
pr = [ur(1)-1; ur(2)-1; ur(3)];
qr = [0; 0; 0];

Appendix D
Nomenclature
Symbol Meaning
] E [
T

Total enzyme concentration (mM )
] E [
OX

Enzyme concentration of the oxygen (mM )
ES] [ Enzyme concentration of the substrate (mM )
] [E
red

Reduced enzyme concentration (mM )
] Med [
OX

Concentration of oxidized mediator at any position in the enzyme layer (mM)
] Med [
red
Concentration of reduced mediator at any position in the enzyme layer (mole cm
3
)
M
D
Diffusion coefficient of oxidized mediator (cm
2
s
-1
)
S
D
Diffusion coefficient of substrate (cm
2
s
-1
)
d Thickness of the planar matrix (cm)
Int. J. Modern Math. Sci. 2014, 10(3): 201-219

Copyright 2014 by Modern Scientific Press Company, Florida, USA
219
b OX
] Med [
Oxidized mediator concentration at the enzyme layer electrode boundary (mM )

] Med [
OX

Oxidized mediator concentration in bulk solution (mM)
] S [ Concentration of substrate at any position in the enzyme layer (mM)
b
] S [
Substrate concentration at the enzyme layer| electrode boundary (mM )

] [S
Substrate concentration in bulk solution (mM)
1
k ,
3
k ,
4
k
Rate constants ( M
-1
s
-1
)
1
k ,
2
k
Rate constants ( s
-1
)
S
B
0
B
Normalized surface concentration of the oxidized mediator
Greek Symbols
2
|
Thiele modulus for the oxidized mediator (none)
S

Dimensionless parameter
Subscripts
OX

Oxidized
T
Total
red
Reduced
o
Oxygen
S
Substrate
P
Product
R
Reduced
b
boundry

Bulk

Вам также может понравиться