Теоретична оцінка електроаналітичного визначення сукралози на полімерному електроді, модифікованому сафраніном
For the first time, sucralose cathodic electrochemical determination, assisted by the safranine-modified electrode has been theoretically described. The correspondent mathematical model has shown that the steady-state stability range is wider than in the most system of electrochemical determination...
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V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
2021
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| author | Tkach, Volodymyr V. Storoshchuk, Nataliia M. Oliveira, Sílvio C. de Ivanushko, Yana G. Nazymok, Yevgeniya V. Luganska, Olga V. Yagodynets, Petro I. |
| author_facet | Tkach, Volodymyr V. Storoshchuk, Nataliia M. Oliveira, Sílvio C. de Ivanushko, Yana G. Nazymok, Yevgeniya V. Luganska, Olga V. Yagodynets, Petro I. |
| author_institution_txt_mv | [
{
"author": "Volodymyr V. Tkach",
"institution": "Yuriy Fedkovich Chernivtsi National University, 2 Kotsiubynsky St., Chernivtsi, 58012, Ukraine; Universidade Federal de Mato Grosso do Sul, Ave. Sen. Felinto. Müller, 1555, C\/P. 549, 79074-460, Campo Grande, MS, Brazil"
},
{
"author": "Nataliia M. Storoshchuk",
"institution": "Yuriy Fedkovich Chernivtsi National University, 2 Kotsiubynsky St., Chernivtsi, 58012, Ukraine"
},
{
"author": "Sílvio C. de Oliveira",
"institution": "Universidade Federal de Mato Grosso do Sul, Ave. Sen. Felinto. Müller, 1555, C\/P. 549, 79074-460, Campo Grande, MS, Brazil"
},
{
"author": "Yana G. Ivanushko",
"institution": "Bukovinian State Medical University, 9 Teatralna Sq., Chernivtsi, 58000, Ukraine"
},
{
"author": "Yevgeniya V. Nazymok",
"institution": "Bukovinian State Medical University, 9 Teatralna Sq., Chernivtsi, 58000, Ukraine"
},
{
"author": "Olga V. Luganska",
"institution": "Zaporizhzhya National University, 66 Zhukovskogo St., Zaporizhzhya, 69600, Ukraine"
},
{
"author": "Petro I. Yagodynets",
"institution": "Yuriy Fedkovich Chernivtsi National University, 2 Kotsiubynsky St., Chernivtsi, 58012, Ukraine"
}
] |
| author_sort | Tkach, Volodymyr V. |
| baseUrl_str | https://bioorganica.com.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-19T14:56:53Z |
| description | For the first time, sucralose cathodic electrochemical determination, assisted by the safranine-modified electrode has been theoretically described. The correspondent mathematical model has shown that the steady-state stability range is wider than in the most system of electrochemical determination over the pyridinic nitrogen-containing conducting polymer. Moreover, the oscillatory behavior is less probable. Therefore, poly(safranine) is an efficient electrode modifier for sucralose electrochemical determination. |
| doi_str_mv | 10.15407/bioorganica2021.02.034 |
| first_indexed | 2025-07-17T12:19:32Z |
| format | Article |
| fulltext |
ISSN 1814-9758. Ukr. Bioorg. Acta, 2021, Vol. 16, N 2
UDC 544.6 + 541.138.3: 539.2: 539.216
DOI: https://doi.org/10.15407/bioorganica2021.02.034
34
Ukrainica Bioorganica Acta
www.bi oorgan ica .org .ua
SHORT COMMUNICATION
The theoretical description for the sucralose electrochemical
determination, assisted by poly(safranine) modified electrode
Volodymyr V. Tkach1,2*, Nataliia M. Storoshchuk1, Sílvio C. de Oliveira2, Yana G. Ivanushko3,
Yevgeniya V. Nazymok3, Olga V. Luganska4, Petro I. Yagodynets1
1 Yuriy Fedkovich Chernivtsi National University, 2 Kotsiubynsky St., Chernivtsi, 58012, Ukraine
2 Universidade Federal de Mato Grosso do Sul, Ave. Sen. Felinto. Müller, 1555, C/P. 549, 79074-460, Campo Grande, MS, Brazil
3 Bukovinian State Medical University, 9 Teatralna Sq., Chernivtsi, 58000, Ukraine
4 Zaporizhzhya National University, 66 Zhukovskogo St., Zaporizhzhya, 69600, Ukraine
Abstract: For the first time, sucralose cathodic electrochemical determination, assisted by the safranine-modified electrode has been
theoretically described. The correspondent mathematical model has shown that the steady-state stability range is wider than in the most
system of electrochemical determination over the pyridinic nitrogen-containing conducting polymer. Moreover, the oscillatory behavior is
less probable. Therefore, poly(safranine) is an efficient electrode modifier for sucralose electrochemical determination.
Keywords: sucralose; conducting polymer; safranine; electrochemical sensors; stable steady-state.
Introduction
The use of chemically modified electrodes (CMEs) is a
very important step in electroanalytical chemistry [1-4].
Compared to bare electrodes, they have some advantages,
such as:
• Rapidity;
• Low cost;
• Exactitude;
• Flexibility;
• Versatility in use;
• Affinity between electrode modifier and analyte.
On the other hand, sucralose [5, 6] is one of the most
used sugar substitutes in the world. It is three times sweeter
than aspartame, two times sweeter than saccharin, and 800-
1000 times sweeter than sucrose [7, 8].
Received:
Revised:
Accepted:
Published online:
15.10.2021
29.10.2021
30.11.2021
30.12.2021
Corresponding author. Tel.: +380-50-640-0359;
e-mail: nightwatcher2401@gmail.com (V. V. Tkach)
ORCID: 0000-0001-7696-0954
Figure 1. The chemical structure of Sucralose.
Sucralose has been approved for use in the US, Canada,
Australia and the European Union [8]. According to its
chemical structure, it belongs to carbohydrates. But, the
presence of three chlorine atoms can cause a toxic effects
like mutagenesis, carcinogenesis, provoke obesity and
growth of glycosis levels [7-12]. Moreover, if stored
improperly, it can form dioxines, even more toxic
compounds [13, 14]. The decomposition of sucralose during
baking can lead to the formation of chloropropanoles [15].
Thus, the development of an efficient method for the
detection of sucralose is really important [16-18], and the
use of electrochemical methods for this would be very
interesting.
© Tkach V. V. et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted
use, distribution, and reproduction in any medium, provided the original author and source are credited.
V. V. Tkach, N. M. Storoshchuk et al.
35
The possibility of the electrochemical determination of
sucralose was already provided theoretically [19-21] and
experimentally confirmed [22]. A direct electrooxidation of
sucralose was used either in the model or in the experiment.
In [19], the immobilization of sucralose on an acridine
derivative capable of forming a quaternary salt was
proposed. It was assumed that the immobilization of
sucralose would be followed by the electrochemical
oxidation of the hydroxyl groups of the sucralose units.
Another possibility may be the electrochemical reduction of
the sucralose salt with the corresponding pyridine nitrogen
compound, in which the safranine polymer can be used as a
modifier [23-25].
However, the use of new electrode modifiers with new
analytes may be impeded by:
• uncertainty about the exact mechanism of the
electrochemical reaction;
• the importance to determine the range of parameters
corresponding to the most efficient active substance
and mediating action;
• the presence of electrochemical instabilities,
described for the electrooxidation and reduction of
organic compounds [26-28].
These problems can only be solved by analyzing a
mathematical model that can adequately describe the
electrochemical determination of fluoxetine. Moreover, it is
also able compare the behavior of this system with the
behavior of similar ones without any experimental essay.
Thus, the purpose of this work is a theoretical and
mechanistic analysis of the electrochemical determination
of sucralose on a conductive polymer containing pyridine
nitrogen atoms. To achieve these goals, we are implement-
ting:
• an assumption about the mechanism of the reaction
consequence leading to the appearance of an
analytical signal;
• development of a mathematical model of the balance
equation corresponding to the electroanalytical
system;
• analysis and interpretation of the model in terms of
electroanalytical use of the system;
• search for the possibility of occurrence of
electrochemical instabilities and factors that cause
them;
• comparison of the behavior of the specified system
with the similar ones [19-21].
System and its Modeling
The safranine fragment, which is already present as a
monosalt, reacts with sucralose at the second nitrogen atom
in the ring to form a biquaternized derivative, which is
thereby reduced electrochemically. The electrochemical
conductivity of the polymer augments by reacting with
sucralose and diminishes at the electrochemical stage.
Schematically, the electrochemical determination of
sucralose on a cathode modified with poly(safranine) will
be described in Figure 2:
Figure 2. Immobilization of sucralose on safranine and electroche-
mical reduction of its salt.
Taking this into account, to describe the system´s
behavior in the potentiostatic mode, we introduce two
options:
s - sucralose concentration in the pre-surface layer;
p - degree of surface coverage with poly(safranine)
sucralose salt.
To simplify the modeling, we suppose that the reactor is
intensively stirred, so the convective flow can be neglected.
We also assume that the background electrolyte is in excess,
so we can neglect the migration flow. The diffusion layer is
supposed to have a constant thickness, equal to δ, and the
concentration profile in it is supposed to be linear.
It can be shown that the behavior of this system will be
described by two balance equations written as:
{
𝑑𝑠
𝑑𝑡
=
2
𝛿
(
𝛴
𝛿
(𝑠0 − 𝑠) − 𝑟𝑠)
𝑑𝑝
𝑑𝑡
=
1
𝑃
(𝑟𝑆 − 𝑟𝑟)
(1)
Herein, 𝛴 is the diffusion coefficient of sucralose, 𝑠0 is
the volume concentration of sucralose, P is the maximal
surface concentration of poly(safranine), and the parameters
r are the correspondent reaction rates, calculated as:
𝑟𝑟 = 𝑘𝑟𝑝𝑛 exp (−
𝑛𝐹𝜑0
𝑅𝑇
) (2)
𝑟𝑠 = 𝑘𝑠(1 − 𝑝)𝑠𝑛 exp(−𝑎𝑠) (3)
Herein, the parameters k are the corresponding reaction
rates n is the number of safranine fragments, capable of
reacting with sucralose, a is the parameter characterizing the
DEL influence of the chemical stage, F is the Faraday
number, 𝜑0 is the potential slope, related to the zero-charge
potential, R is the universal gas constant, and T is the
absolute temperature.
Results and Discussion
In order to describe the behavior of the electroanalytical
determination of sucralose over a poly(safranine)-modified
electrode, we analyze the equation-set (1) by means of
linear stability theory and bifurcation analysis. The steady-
state Jacobian matrix members for this system may be
described as:
(
𝑎11 𝑎12
𝑎21 𝑎22
) (4)
ISSN 1814-9758. Ukr. Bioorg. Acta, 2021, Vol. 16, N 2
36
where:
𝑎11 =
2
𝛿
(−
𝛴
𝛿
− 𝑛𝑘𝑠(1 − 𝑝)𝑠𝑛−1 exp(−𝑎𝑠) +
𝑎𝑘𝑠(1 − 𝑝)𝑠𝑛 exp(−𝑎𝑠)) (5)
𝑎12 =
2
𝛿
(𝑘𝑠𝑠𝑛 exp(−𝑎𝑠)) (6)
𝑎21 =
1
𝑃
(𝑛𝑘𝑠(1 − 𝑝)𝑠𝑛−1 exp(−𝑎𝑠) −
𝑎𝑘𝑠(1 − 𝑝)𝑠𝑛 exp(−𝑎𝑠)) (7)
𝑎22 =
1
𝑃
(−𝑘𝑠𝑠𝑛 exp(−𝑎𝑠) − 𝑛𝑘𝑟𝑝𝑛−1 exp (−
𝑛𝐹𝜑0
𝑅𝑇
) +
𝑗𝑘𝑟𝑝𝑛 exp (−
𝑛𝐹𝜑0
𝑅𝑇
)) (8)
General conditions for singular points for bivariant
systems are presented in the Table 1.
Table 1. The basic conditions for singular points for the
bivariant systems.
Stable steady-state Tr J<0, Det J>0
Oscillatory behavior Tr J=0, Det J>0
Monotonic instability Tr J<0, Det J=0
Avoiding cumbersome expressions, we introduce new
variables, rewriting the determinant as (9)
2
𝛿𝐶
|−𝜅 − 𝑌 𝛬
𝑌 −𝛬 − 𝛺
| (9)
Taking into account the elements (5) and (8), the
appearance of oscillatory behavior is possible in this
system. The main Hopf bifurcation condition is realized if
the main diagonal contains positive elements related to the
positive callback.
In this system, there are two elements responsible for the
oscillatory behavior
+𝑎𝑘𝑠(1 − 𝑝)𝑠𝑛 exp(−𝑎𝑠) > 0, if a>0
and 𝑗𝑘𝑟𝑝𝑛 exp (−
𝑛𝐹𝜑0
𝑅𝑇
) > 0, if j>0,
describing the DEL influences of chemical and
electrochemical stages, respectively. The probability of the
oscillatory behavior is more expressed than in the simplest
cases, but less expressed than in some similar systems [21].
All of the mentioned elements depend on the composition
of the background electrolyte, as well as on the amplitude
and frequency of oscillations. Mathematically, the condition
of oscillatory behavior will be described as (10):
{
2
𝛿
(−𝜅 − 𝑌) +
1
𝑃
(−𝛬 − 𝛺) = 0
2
𝛿𝐶
(𝜅𝛬 + 𝜅𝛺 + 𝛶𝛺) > 0
(10)
However, if the mentioned elements are negative, the
steady-state stability will be obtained. Opening the brackets
and applying the stability requisite, we obtain the steady-
state stability condition, which can be described as (11):
{
2
𝛿
(−𝜅 − 𝑌) +
1
𝑃
(−𝛬 − 𝛺) < 0
2
𝛿𝐶
(𝜅𝛬 + 𝜅𝛺 + 𝛶𝛺) > 0
(11)
And defines a diffusion-controlled system effictive for
the determination of sucralose over poly(safranine) in a
potentiostatic mode. This condition is satisfied in a
relatively wide range of parameters, in which the
dependence between the electrode current and copper
concentration will be linear.
The monotonic instability corresponding to the detection
limit separates stationary stable-states from unstable states.
Its condition is mathematically expressed as (12):
{
2
𝛿
(−𝜅 − 𝑌) +
1
𝑃
(−𝛬 − 𝛺) < 0
2
𝛿𝐶
(𝜅𝛬 + 𝜅𝛺 + 𝛶𝛺) > 0
(12)
This model is applicable to the determination of
sucralose in a neutral enviroment. In acidic media, protons
strongly interfere with the electroanalytical process, so a
trivariant model has to be used. This model will be
described in our next work.
Conclusions
From the theoretical description of the electrochemical
determination of sucralose over poly(safranine), we can
conclude:
• The mechanism consists of chemical and
electrochemical stages leading to a well-defined
analytical signal. The polymer can serve as an
excellent modifier for the quantitative determination of
sucralose. A stable steady-state is easily maintained;
• The system is a diffusion-controlled electroana-
lytically efficient process;
• In this system, oscillatory behavior is possible, due
only to the DEL influences of both electrochemical
processes and the chemical stage.
Notes
The authors declare no conflict of interest.
Author contributions. The manuscript was written
through contributions of all authors. All authors have given
approval to the final version of the manuscript.
V. V. Tkach, N. M. Storoshchuk et al.
37
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Теоретична оцінка електроаналітичного визначення сукралози на полімерному
електроді, модифікованому сафраніном
В. В. Ткач1,2*, Н. М. Сторощук1, С. С. де Олівейра2, Я. Г. Іванушко3, Є. В. Назимок3, О. В. Луганська4,
П. І. Ягодинець1
1 Чернівецький національний університет імені Юрія Федьковича, вул. Коцюбинського, 2, Чернівці, 58012, Україна
2 Федеральний університет штату Мату-Ґросу- ду-Сул, просп. Сенадора Філінто Мюллера, 1555, Кампу-Гранді, Мату-Ґросу-ду-Сул,
79074-460, Бразилія
3 Буковинський державний медичний університет, пл. Театральна, 2, Чернівці, 58002, Україна
4 Запорізький національний університет, вул. Жуковського, 66, Запоріжжя, 69600, Україна
Резюме: Вперше з теоретичної точки зору розглядається можливість електрохімічного визначення сукралози за допомогою модифікованого
сафраніном електрода. Аналіз математичної моделі показав, що стаціонарний діапазон стабільності є ширшим, ніж у більшості систем
електрохімічного визначення з піридиновим полімерним провідником. Таким чином, полі(сафранін) є ефективним електродним модифікатором.
Ключові слова: сукралоза; провідний полімер; сафранін; електрохімічні сенсори; стійкий стаціонарний стан.
Notes
|
| id | oai:ojs2.bioorganica.com.ua:article-25 |
| institution | Ukrainica Bioorganica Acta |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-20T01:00:39Z |
| publishDate | 2021 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | bioorganicacomua/02/9cc41aa8aa5b4abcbdabcb289b3c2802.pdf |
| spelling | oai:ojs2.bioorganica.com.ua:article-252026-07-19T14:56:53Z The theoretical description for the sucralose electrochemical determination, assisted by poly(safranine) modified electrode Теоретична оцінка електроаналітичного визначення сукралози на полімерному електроді, модифікованому сафраніном Tkach, Volodymyr V. Storoshchuk, Nataliia M. Oliveira, Sílvio C. de Ivanushko, Yana G. Nazymok, Yevgeniya V. Luganska, Olga V. Yagodynets, Petro I. sucralose conducting polymer safranine electrochemical sensors stable steady-state сукралоза провідний полімер сафранін електрохімічні сенсори стійкий стаціонарний стан For the first time, sucralose cathodic electrochemical determination, assisted by the safranine-modified electrode has been theoretically described. The correspondent mathematical model has shown that the steady-state stability range is wider than in the most system of electrochemical determination over the pyridinic nitrogen-containing conducting polymer. Moreover, the oscillatory behavior is less probable. Therefore, poly(safranine) is an efficient electrode modifier for sucralose electrochemical determination. Вперше з теоретичної точки зору розглядається можливість електрохімічного визначення сукралози за допомогою модифікованого сафраніном електрода. Аналіз математичної моделі показав, що стаціонарний діапазон стабільності є ширшим, ніж у більшості систем електрохімічного визначення з піридиновим полімерним провідником. Таким чином, полі(сафранін) є ефективним електродним модифікатором. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2021-12-27 Article Article application/pdf https://bioorganica.com.ua/index.php/journal/article/view/25 10.15407/bioorganica2021.02.034 Ukrainica Bioorganica Acta; Vol. 16 No. 2 (2021): Ukrainica Bioorganica Acta; 34-37 Ukrainica Bioorganica Acta; Том 16 № 2 (2021): Ukrainica Bioorganica Acta; 34-37 1814-9766 1814-9758 10.15407/bioorganica2021.02 en https://bioorganica.com.ua/index.php/journal/article/view/25/30 Copyright (c) 2021 Volodymyr V. Tkach, Nataliia M. Storoshchuk, Sílvio C. de Oliveira, Yana G. Ivanushko, Yevgeniya V. Nazymok, Olga V. Luganska, Petro I. Yagodynets https://creativecommons.org/licenses/by/4.0 |
| spellingShingle | сукралоза провідний полімер сафранін електрохімічні сенсори стійкий стаціонарний стан Tkach, Volodymyr V. Storoshchuk, Nataliia M. Oliveira, Sílvio C. de Ivanushko, Yana G. Nazymok, Yevgeniya V. Luganska, Olga V. Yagodynets, Petro I. Теоретична оцінка електроаналітичного визначення сукралози на полімерному електроді, модифікованому сафраніном |
| title | Теоретична оцінка електроаналітичного визначення сукралози на полімерному електроді, модифікованому сафраніном |
| title_alt | The theoretical description for the sucralose electrochemical determination, assisted by poly(safranine) modified electrode |
| title_full | Теоретична оцінка електроаналітичного визначення сукралози на полімерному електроді, модифікованому сафраніном |
| title_fullStr | Теоретична оцінка електроаналітичного визначення сукралози на полімерному електроді, модифікованому сафраніном |
| title_full_unstemmed | Теоретична оцінка електроаналітичного визначення сукралози на полімерному електроді, модифікованому сафраніном |
| title_short | Теоретична оцінка електроаналітичного визначення сукралози на полімерному електроді, модифікованому сафраніном |
| title_sort | теоретична оцінка електроаналітичного визначення сукралози на полімерному електроді, модифікованому сафраніном |
| topic | сукралоза провідний полімер сафранін електрохімічні сенсори стійкий стаціонарний стан |
| topic_facet | sucralose conducting polymer safranine electrochemical sensors stable steady-state сукралоза провідний полімер сафранін електрохімічні сенсори стійкий стаціонарний стан |
| url | https://bioorganica.com.ua/index.php/journal/article/view/25 |
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