PHYSICAL CHEMISTRY

MATHEMATICAL MODEL FOR THE AUTOCATALYTIC REACTIONS

IN THE VISUAL PIGMENTS DYNAMICS

IRINA AGACHI, M. IGNAT, D. E. CREANGA

“Al I. Cuza” University of Iaºi, Faculty of Physics, 11a, Blvd. Carol I, Iaºi, Romania,
e-mail:bcirina@k.ro
Received December 21, 2004

This study is focused on the modeling of the photosensitive pigments

dynamics in some superior insects, considering some modifications to the closed
cycle of transformations, with many parallel branches, provided by literature reports.
The brusselator model has been applied in order to discuss a simplified case of
rhodopsine- metarhodopsine autocatalytic transformations.
Key words: interchangeable pigment system, stability discussion, limit cycle.

1. INTRODUCTION

The study of the dipteran eye (superior insects represented by Drosophila

melanogaster, Musca domestica, etc.) represents an interesting alternative for the
indirect investigation of the human eye, since:
– the anatomical organization is parallel to that of the human eye but with a
more simplified set of neurons;
– the experimental study is easier, especially for electrophysiological
investigations, the visual cells being larger, the insect retinula being not a
compact tissue as the human retina and the various types of potassium ion
channels from the visual cell membranes being very well represented [1].
Regarding the periodic transformation of rhodopsine into metarhodopsine
under the influence of light stimuli, the next model was proposed in the literature.
According to this schema, proposed on the basis of various experimental
evidences, the dark form of rhodopsine, after the absorption of a blue light
photon, turns into another compound, X (lumi-rhodopsine according to [3]
which further becomes energized metarhodopsine, M*. This one can be reversed
into rhodopsine after the absorption of an orange photon (though the
intermediate compound Y). But the M* molecules can also transform into a
storage form, M0 or in the low energized form, M. The reaction rate constants t2
and t3 are found to be smaller than t 1. The arrows denoted the processes directly


Paper presented at the 5th International Balkan Workshop on Applied Physics, 5–7 July
2004, Constanþa, Romania.

Rom. Journ. Phys., Vol. 50, Nos. 9– 1 0 , P. 1113–1118, Bucharest, 2005

1114 Irina Agachi, M. Ignat, D. E. Creanga 2

Fig. 1. – The pigment

transformation in the superior
insects [2]. R– rhodopsine,
dark form; X, Y –
intermediate pigment forms;
M* – metharhodopsine in the
excited state; M0 –
metarhodopsine in the storage
form; M – metarhodopsine in
low energetic state; ti – rate
constants; E – metabolic
energy; S – membrane situs
in the visual cell; R′–
rhodopsine obtainable on the
metabolic energy basis.

controlled by light absorption while dashed lines refers to the transformations

based on metabolic energy (provided by the macroergic molecules). The
intermediate compound Y (bato-rhodopsine according also to [3]) can appear
during the transformation of M into R′, while the X compound is supposed to
intermediate the transformation of R′ into M.
In the present article a certain cyclic transformation is taken into discussion
by means of the brusselator theoretical model.

2. THEORETICAL BACKGROUND

The brusselator model was developed by Ilia Prigogine and co. (Nobel Prize,
1977) in order to describe the autocatalytic oscillations ubiquitous in the nature,
especially in the living bodies. The brusselator reaction equations are the next:

A ⎯⎯
k1
→X

2X + Y ⎯⎯
k2
→ 3X

B + X ⎯⎯
k
3
→D + Y

X ⎯⎯
k4
→E

where A and B are the reactants, X and Y are intermediate products while D and
E are the final products, k1, …, k4 being the reaction rate constants [4]. The
evolution of the compounds X and Y is given by the equations:
3 Autocatalytic reactions in the visual pigments dynamics 1115

dX = k A + k X 2 Y − k BX − k X
1 2 3 4
dt
dY = − k X 2 Y + k BX .
2 3
dt
Introducing adimensional variables, a, b, x, y, τ and considering all
coefficients equal to the unit one can obtain the equation system:
dx = a + x 2 y − bx − x
dτ
dy
= − x 2 y + bx
dτ
having the stationary solution:
x0 = a

y0 = b .
a
The stability of this system solution may be discussed by taking the general
solution of the form:
x = a + α exp(λτ)

y = b + β exp(λτ)
a
with the conditions:
α << a , β << b .
a
The characteristic equation is obtained in the form (linear approximation):

λ 2 + ( a2 + 1 − b ) λ + a2 = 0
having the solutions:

λ1 ,2 = − −a + 1 − b ± 1 ( a2 + 1 − b )
2 2
− 4 a2 .
2 2
When these solutions are complex numbers, the relation between ‘a’ and ‘b’ is
leading to several distinct regions in the plane (a, b). In the region IV the
exponential increase has high amplitude and repeated periodically [5] so that a
limit cycle appears in the plane (x, y). The differential equations that describe the
kinetics of these reactions are:
dy
= − x 2 y + bx
dt
1116 Irina Agachi, M. Ignat, D. E. Creanga 4

dx = a + x 2 y − bx
dt
a and b being parameters that depend of R and Y concentrations.

Fig. 2. – Left: the four regions in the plane (a, b) are regions of stability and instability. Right:
the limit cycle in the plane (x, y).

3. THE NEW MODEL AND THE DISCUSSION

The phenomenological model is discussed inhere (Fig. 3) considering the

cycle of rhodopsine transformations with additional notations for the
transformation ways (1,…, 8). The parallel with the brusselator system may be
done if the equivalent notations below are applied:

A X Y B D E
M* Y0 R′ M X0 R

The transformation scheme is detailed as follows:

M * ⎯⎯
1→ Y and M* ⎯⎯ 4′ → Y similarly with: A → X;
2 → M ⎯⎯
0 0 0
2′′ → R ⎯⎯
Y0 ⎯⎯ 3′ → X ⎯⎯
3 → M * ⎯⎯ 4′ → M ⎯⎯
2 → M ⎯⎯ 5→ Y ;
0 0 0

Y0 ⎯⎯ 3′ → X ⎯⎯
3 → R ⎯⎯ 3′′ → M * ⎯⎯
4 → M ⎯⎯
5→ Y ;
0 0

R′ ⎯⎯ 6′ → M ⎯⎯
6 → X ⎯⎯ 5→ Y ;
0 0

Which is similarly with 2X + Y → 3X .

5 Autocatalytic reactions in the visual pigments dynamics 1117

Fig. 3. – The transformation

scheme with addition notations.

Further: Y0 ⎯⎯ 7′ → R ′, M ⎯⎯
7 → R ′, R ′ ⎯⎯
6 → X which, after summation,
0
is similar to: B + X → D + Y.
Finally: R′ ⎯⎯8 → R is similarly to X → E.

So, the rhodopsine transformation is identified with a brusselator

mechanism and the differential equations presented bellow can be applied.
The solution of the last equation system can be computationally
represented as in Fig. 4.

Fig. 4. – The 3D representation of

the x,y dependence into the frame of
the proposed model. In plane the
z = constant a cycle limit is
projected, characteristic of the self-
oscillations which may exist in the
system.

This way the autocatalytical character of the rhodopsine conversion into

meta-rhodopsine and reversely can be better understanding as representing a
self-oscillatory system, controlled by the light absorption. The system attractor is
a limit cycle (corresponding to a section of the 3-D representation in Fig. 4).
1118 Irina Agachi, M. Ignat, D. E. Creanga 6

4. CONCLUSIONS

The photochemistry of the superior insect eye is a complex phenomenon

with cyclic character corresponding to the rhodopsine conversion into meta-
rhodopsine under the light action with re-conversion to the dark form molecules.
The intermediate compounds evidenced by means of accurate experimental
investigations are instable molecules contributing to the shaping of the
autocatalytic feature of the rhodopsine transformation. These cyclic
transformations can be approached quantitatively by means of the brusselator
mathematical model.

REFERENCES

1. R. C. Hardie, K. Stavenga, Faces of vision, Springer Verlag, Berlin, 1989, 391–424.

2. W. Hoope, Biophysics, Academic Press, New York, 1980.
3. F. Gremy, J. Perrin, Elements de Biophysique, Flammarion, Paris, 1976.
4. M. Volkenstein, Biophysique, Ed. MIR, Moscow, 1985.
5. I. Bacalu, Ecuatii diferentiale si stabilitate, Ed. Matrix, Bucuresti, 2002.